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1

Spectroscopy and reactions of molecules important in chemical evolution  

NASA Technical Reports Server (NTRS)

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.

1974-01-01

2

Master Equation Models for Chemical Reactions of Importance in Combustion  

Microsoft Academic Search

The master equation provides a quantitative description of the interaction between collisional energy transfer and chemical reaction for dissociation, isomerization, and association processes. The approach is outlined for both irreversible and reversible dissociation, isomerization, and association reactions. There is increasing interest, especially in combustion, in association reactions that involve several linked potential wells, with the possibility of isomerization, collisional stabilization,

Michael J. Pilling; Struan H. Robertson

2003-01-01

3

Chemical Reactions  

NSDL National Science Digital Library

We don't often stop to think about it, but underlying many of our everyday activities are chemical reactions. From the cooking of an egg to the growth of a child, chemical reactions make things happen. Although many of the reactions that support our lives

National Science Teachers Association (NSTA)

2009-05-01

4

Chemical Reactions  

NSDL National Science Digital Library

We are going go over a general view of reactions to prepare us for our unit on Chemical Reactions! Have fun learning! WARNING: If you are caught looking at ANY other site, without permission, you will be sent to the ALC, and you will not participate in any other computer activities for the rest of the year. Get your worksheet and begin! Overview Take this quiz and have me come over and sign off on your worksheet when you have completed the quiz! Overview Quiz Next let's take a look at what effect the rate of a chemical reaction. Rates of Reactions Another quiz, another check off by me! Rates of Reactions Quiz Now how do we measure how fast a ...

Hicken, Mrs.

2009-05-04

5

Chemical Reactions at Surfaces  

Microsoft Academic Search

Chemical reactions at surfaces underlie some of the most important processes of today, including catalysis, energy conversion, microelectronics, human health and the environment. Understanding surface chemical reactions at a fundamental level is at the core of the field of surface science. The Gordon Research Conference on Chemical Reactions at Surfaces is one of the premiere meetings in the field. The

Nancy Ryan Gray Michael Henderson

2010-01-01

6

Importance of cytochromes in cyclization reactions: Quantum chemical study on a model reaction of proguanil to cycloguanil.  

PubMed

Proguanil, an anti-malarial prodrug, undergoes cytochrome P450 catalyzed biotransformation to the pharmacologically active triazine metabolite (cycloguanil), which inhibits plasmodial dihydrofolate reductase. This cyclization is catalyzed by CYP2C19 and many anti-malarial lead compounds are being designed and synthesized to exploit this pathway. Quantum chemical calculations were performed using the model species (Cpd I for active species of cytochrome and N4-isopropyl-N6-methylbiguanide for proguanil) to elucidate the mechanism of the cyclization pathway. The overall reaction involves the loss of a water molecule, and is exothermic by approximately 55 kcal/mol, and involves a barrier of approximately 17 kcal/mol. The plausible reaction pathway involves the initial H-radical abstraction from the isopropyl group by Cpd I, followed by two alternative paths- (i) oxygen rebound to provide hydroxyl derivative and (ii) loss of additional H-radical to yield 1,3,5-triazatriene, which undergoes cyclization. This study helped in understanding the role of the active species of cytochromes in this important cyclization reaction. © 2014 Wiley Periodicals, Inc. PMID:25196060

Arfeen, Minhajul; Patel, Dhilon S; Abbat, Sheenu; Taxak, Nikhil; Bharatam, Prasad V

2014-10-30

7

Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets  

NASA Technical Reports Server (NTRS)

The paper discusses the following: 1. F + Cl2 Kinetics. Absolute rate constant for the reaction F(P-2) with Cl2 has been measured using the discharge flow kinetics technique coupled to mass spectrometric detection at T = 180 - 360 K and 1 Torr He nominal pressure. 2. Vapor pressure system. The main effort on the vapor pressure system involved the design and construction of an insulated enclosure ("Bakeout Box") to improve the uniformity of heating during the bakeout process. 3. Sunphotometer System. This period saw the completion of the two-channel sunphotometer, its calibration, and two field deployments. 4. Vibrational-to-translation (V-T) transfer rates for light hydrocarbons at low temperatures are important parameters in thermal-structure models of the upper atmospheres of the outer planets and their satellites. However, the required data are either simply not available or do not extend to the low temperatures found in those systems. Because methane is such an important constituent in outer planet atmospheres, we have initiated a program to measure the temperature dependence of (V-T) rates for its relaxation by appropriate collision partners. 5. The central focus of this research has been the vapor phase nucleation and growth of metals/refractory species into small particles and the aggregation of these primary particles into larger structures. These topics are part of the broader goal of understanding the conditions under which interstellar dust grains condense from stellar outflows and how these small dust grains coagulate into larger bodies such as planetesimals or planets.

Nesbitt, Fred L.

2003-01-01

8

Microfluidic chemical reaction circuits  

DOEpatents

New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

Lee, Chung-cheng (Irvine, CA); Sui, Guodong (Los Angeles, CA); Elizarov, Arkadij (Valley Village, CA); Kolb, Hartmuth C. (Playa del Rey, CA); Huang, Jiang (San Jose, CA); Heath, James R. (South Pasadena, CA); Phelps, Michael E. (Los Angeles, CA); Quake, Stephen R. (Stanford, CA); Tseng, Hsian-rong (Los Angeles, CA); Wyatt, Paul (Tipperary, IE); Daridon, Antoine (Mont-Sur-Rolle, CH)

2012-06-26

9

Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets  

NASA Technical Reports Server (NTRS)

The methyl self-reaction was studied at T = 298 K and 202 K and at three different pressures, P = 0.5, 1.0, and 2.1 Torr. The experimental measurements were performed in our discharge flow-mass spectrometer (DF-MS) apparatus. The methyl radicals were generated by the reaction of F with methane. Passing a mixture of molecular fluorine, F2, in helium through a microwave cavity generated the atomic fluorine reagent. The atomic F enters the flow tube through a rear port on the flow tube. The methane reagent enters the flow tube through a movable injector located coaxial in the flow tube. The decay of methyl radical signal was monitored at a mass/charge ratio (m/z) of 15 as a function of the injector distance. To minimize secondary chemistry from the reaction CH3 + F to CH2 + HF the initial [CH4](sub 0)/[F](sub 0) was above 37.0 and typically 100. This ensures a 1:1 relationship between initial [F] and [CH3]. A titration of F with excess Cl2 yields the initial [F](sub 0). Our experimental methodology to accurately measure the mass spectrometer scaling factor, i.e., the relationship between initial signal and [CH3](sub 0) has been improved. Now we measure the CH3 signal decay under exponential decay conditions at low initial [F](sub 0), 3x10(exp 11) molecule/cc, in the presence of Cl2. This minimizes the second-order decay contributed by the CH3 self-reaction and a simple extrapolation of the 1n(signal) vs time plot to t = 0 gives the initial signal. This provides the desired relationship between initial signal at 15 amu and [CH3](sub 0). The resulting calibration is then applied to the observed decay of the CH3 signal at high concentrations of CH3 assuming linearity of this scaling factor.

Nesbitt, Fred L.

2001-01-01

10

Categorizing Chemical Reactions  

NSDL National Science Digital Library

Science Objects are two hour on-line interactive inquiry-based content modules that help teachers better understand the science content they teach. This Science Object is the second of four Science Objects in the Chemical Reactions SciPack. It provides an

National Science Teachers Association (NSTA)

2009-07-10

11

Rates of Chemical Reactions  

NSDL National Science Digital Library

Science Objects are two hour on-line interactive inquiry-based content modules that help teachers better understand the science content they teach. This Science Object is the third of four Science Objects in the Chemical Reactions SciPack. It demonstrates

National Science Teachers Association (NSTA)

1900-01-01

12

Basic Chemical Principles 1: Reaction Kinetics  

E-print Network

with radiation can cause chemical events: bonds broken, molecules excited { Creation of radicals Molecular state: Lowest energy con#12;guration of electrons in orbitals #15; To form chemical bond, combine atomic, photo-chemical reactions are important: reactions initiated by light #12; { Interaction of matter

Schofield, Jeremy

13

Chemical Reactions in DSMC  

SciTech Connect

DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

Bird, G. A. [GAB Consulting Pty Ltd, 144/110 Sussex Street, Sydney NSW 2000 (Australia)

2011-05-20

14

Mass Transfer with Chemical Reaction.  

ERIC Educational Resources Information Center

Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

DeCoursey, W. J.

1987-01-01

15

The classification of chemical reactions  

Microsoft Academic Search

The classification and shorthand designation of chemical reactions are considered. It is concluded that single-step reactions can be divided into a finite number of types, each of which could be represented by an unambiguous symbol. The various types are listed and illustrated. Multi-step reactions, however, cannot be classified (in any detail) in a limited number of ways and for such

D. P. N. Satchell

1977-01-01

16

Ionic reactions of atmospheric importance  

NASA Astrophysics Data System (ADS)

A variable-temperature flowing afterglow/Langmuir probe (VT-FALP) apparatus has been used to study several electron-ion dissociative recombination reactions and several electron attachment reactions. Thus the variation with temperature of the respective dissociative recombination coefficients, alpha and electron attachment coefficients, beta have been determined. The recombination studies have included the species O2+, NO+, NH4+, H3, HC0+, N2H+ and CH5+, and the attachment studies have included the species CC14, CC13F, CC12F2, CHC13, C12, SF6, C-C7F14, CH3Br, CF3Br, CH2Br2 and CH3I. Some ion molecule reactions have also been studied as a function of temperature and of ion-molecule center-of mass energy using a variable-temperature selective ion flow drift tube (VT-SIFDT).

Smith, D.; Adams, N.

1984-08-01

17

Chemical burn or reaction  

MedlinePLUS

... the skin has come in contact with the toxic substance Rash , blisters , burns on the skin Unconsciousness ... locked cabinet. Avoid mixing different products that contain toxic chemicals such as ammonia and bleach. The mixture ...

18

Ionic reactions of atmospheric importance  

NASA Astrophysics Data System (ADS)

A variable-temperature flowing afterglow/Langmuir probe (FALP) apparatus has been used to study the temperature dependence of a number of electron-ion dissociative recombination coefficients, alpha e, and electron attachment coefficients, Beta, over the temperature range 200-600 K. Thus alpha e(02(+)), alpha e(NO+)) and alpha e(NH4+)) have been shown to vary inversely with temperature, T, as alpha e approximately T to the -n power with n = 0.7, 0.9 and 0.6 respectively. Alpha e(H30+)) was found to be independent of temperature. Beta(CC14), Beta(CC13F) and Beta (SF6) were all very large, close to their theoretical maximum values (approximately .0000004 cc/s at 300 K) and varied only very slowly with temperature over the available range, whereas Beta(CC12F2), Beta(CHC13) and Beta(C12) were smaller and increased appreciably with temperature. From the data, activation energies, Ea, were obtained for the dissociative attachment reactions of CC13F, CC12F2, CHC13 and C12. Thus Ea(CC13F) approximately 0.02eV, Ea(CC12F2) approximately 0.15eV, Ea(CHC13) approximately 0.12 eV and Ea(C12) approximately 0.05 eV.

Smith, D.; Adams, N. G.

1983-11-01

19

LEGO® Chemical Reactions  

NSDL National Science Digital Library

This activity uses LEGO® bricks to represent atoms bonding into molecules and crystals. The lesson plan is for a 2.5 hour workshop (or four 45-minute classes). There is a "wet lab" chemistry experiment (mixing baking soda and calcium chloride with phenol red indicator), followed by a "LEGO lab" modeling phase that includes writing formulas using chemical notation. This lesson is also offered as a 2.5 hour field trip lesson at the MIT Edgerton Center.

Vandiver, Kathleen M.

2009-01-01

20

Kinematically complete chemical reaction dynamics  

NASA Astrophysics Data System (ADS)

Kinematically complete studies of molecular reactions offer an unprecedented level of insight into the dynamics and the different mechanisms by which chemical reactions occur. We have developed a scheme to study ion-molecule reactions by velocity map imaging at very low collision energies. Results for the elementary nucleophilic substitution (SN2) reaction Cl- + CH3I ? ClCH3 + I- are presented and compared to high-level direct dynamics trajectory calculations. Furthermore, an improved design of the crossed-beam imaging spectrometer with full three-dimensional measurement capabilities is discussed and characterization measurements using photoionization of NH3 and photodissociation of CH3I are presented.

Trippel, S.; Stei, M.; Otto, R.; Hlavenka, P.; Mikosch, J.; Eichhorn, C.; Lourderaj, U.; Zhang, J. X.; Hase, W. L.; Weidemüller, M.; Wester, R.

2009-11-01

21

Homeostasis in Chemical Reaction Pathways  

E-print Network

We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

V. A. Malyshev; A. D. Manita; A. A. Zamyatin

2011-12-25

22

Homeostasis in Chemical Reaction Pathways  

E-print Network

We consider stochastic models of chemical reaction networks with time dependent input rates and several types of molecules. We prove that, in despite of strong time dependence of input rates, there is a kind of homeostasis phenomenon: far away from input nodes the mean numbers of molecules of each type become approximately constant (do not depend on time).

Malyshev, V A; Zamyatin, A A

2011-01-01

23

Spectroscopic and photochemical study of molecules important in chemical evolution  

NASA Technical Reports Server (NTRS)

The primary broad goals of this research are to investigate (1) the possible reactions responsible for generation of compounds important in chemical evolution, and (2) reactions of compounds important in chemical evolution. In both cases the interest includes molecules that exist in interstellar space as well as those present on or near other planets and those which were thought to be present on or near the primitive earth.

Becker, R. S.

1973-01-01

24

Strain-induced chemical reactions  

SciTech Connect

The uniaxial displacements at leading edges of detonation fronts in solids create large shear-strains. These bend the covalent bonds, and cause piezoelectric effects, thereby closing the HOMO-LUMO energy gaps, and leading to ultra-fast athermal chemical reactions. Specific examples are discussed: ammonium, azide, and nitrate ions; and PETN. It is shown that their properties are consistent with the proposed mechanism. [copyright]American Institute of Physics

Gilman, J.J. (Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States))

1994-07-10

25

Theoretical studies of chemical reaction dynamics  

SciTech Connect

This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

Schatz, G.C. [Argonne National Laboratory, IL (United States)

1993-12-01

26

Chemical reactions at aqueous interfaces  

NASA Astrophysics Data System (ADS)

Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1) Adsorption of dilute PFOS(aq) and PFOA(aq) to acoustically cavitating bubble interfaces was greater than equilibrium expectations due to high-velocity bubble radial oscillations; 2) Relative ozone oxidation kinetics of aqueous iodide, sulfite, and thiosulfate were at variance with previously reported bulk aqueous kinetics; 3) Organics that directly chelated with the anode surface were oxidized by direct electron transfer, resulting in immediate carbon dioxide production but slower overall oxidation kinetics. Chemical reactions at aqueous interfaces can be the rate-limiting step of a reaction network and often display novel mechanisms and kinetics as compared to homogeneous chemistry.

Vecitis, Chad David

27

Plasmon-driven sequential chemical reactions in an aqueous environment  

PubMed Central

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight. PMID:24958029

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-01-01

28

Quantum Theory of Fast Chemical Reactions  

SciTech Connect

The aims of the research under this grant were to develop a theoretical understanding and predictive abiility for a variety of processes occurring in the gas phase. These included bimolecular chemical exchange reactions, photodissociation, predissociation resonances, unimolecular reactions and recombination reactions. In general we assumed a knowledge, from quantum chemistry, of the interactions of the atoms and molecular fragments involved. Our focus was primarily on the accurate (quantum) dynamics of small molecular systems. This has been important for many reactions related to combustion and atmospheric chemistry involving light atom transfer reactions and, for example, resonances in dissociation and recombination reactions. The rates of such reactions, as functions of temperature, internal states, and radiation (light), are fundamental for generating models of overall combustion processes. A number of new approaches to these problems were developed inclluding the use of discrete variable representations (DVR's) for evaluating rate constants with the flux-flux correlation approach, finite range approaches to exact quantum scattering calculations, energy selected basis representations, transition state wave packet approaches and improved semiclassical approaches. These (and others) were applied to a number of reactive systems and molecular systems of interest including (many years ago) the isotopic H + H2 exchange reactions, the H2 + OH (and H + H2O) systems, Ozone resonances, van der Waals molecule reactions, etc. A total of 7 graduate students, and 5 post-doctoral Research Associates were supported, at least in part, under this grant and seven papers were published with a total of 10 external collaborators. The majority of the 36 publications under this grant were supported entirely by DOE.

John C. Light

2007-07-30

29

Laser-initiated chemical chain reactions  

Microsoft Academic Search

A detailed kinetic and experimental analysis is presented for chemical chain reaction processes initiated by well-controlled, low power laser pulses. Realtime evolution of the chain reaction is followed by direct detection of infrared chemiluminescence from vibrationally excited HCl product molecules produced by one of the propagation reactions in the chain. By appropriate choice of conditions, the chain reactions may be

David J. Nesbitt; Stephen R. Leone

1980-01-01

30

2005 Chemical Reactions at Surfaces  

SciTech Connect

The Gordon Research Conference (GRC) on 2005 Chemical Reactions at Surfaces was held at Ventura Beach Marriott, Ventura California from February 13, 2005 through February 18, 2005. The Conference was well-attended with 124 participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. In designing the formal speakers program, emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions. In order that more scientists could communicate their most recent results, poster presentation time was scheduled. Attached is a copy of the formal schedule and speaker program and the poster program. In addition to these formal interactions, 'free time' was scheduled to allow informal discussions. Such discussions are fostering new collaborations and joint efforts in the field.

Cynthia M. Friend

2006-03-14

31

Microfabricated electrochemiluminescence cell for chemical reaction detection  

DOEpatents

A detector cell for a silicon-based or non-silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The detector cell is an electrochemiluminescence cell constructed of layers of silicon with a cover layer of glass, with spaced electrodes located intermediate various layers forming the cell. The cell includes a cavity formed therein and fluid inlets for directing reaction fluid therein. The reaction chamber and detector cell may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The ECL cell may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

Northrup, M. Allen (Berkeley, CA); Hsueh, Yun-Tai (Davis, CA); Smith, Rosemary L. (Davis, CA)

2003-01-01

32

Chemical Kinetics: Rate of Reaction  

NSDL National Science Digital Library

This site offers an interactive tutorial that emphasizes graphical interpretation of chemical kinetics. The stoichiometric coefficients for a chemical equation are determined by comparing the slopes of concentration-time plots for the reactants and products. This tutorial is coupled to others to further guide the student to a better understanding of chemical kinetics.

Blauch, David N.

33

A Unified Theory of Chemical Reactions  

E-print Network

We propose a new and general formalism for elementary chemical reactions where quantum electronic variables are used as reaction coordinates. This formalism is in principle applicable to all kinds of chemical reactions ionic or covalent. Our theory reveals the existence of an intermediate situation between ionic and covalent which may be almost barrierless and isoenegetic and which should be of high interest for understanding biochemistry.

Aubry, S

2014-01-01

34

'GREENER' CHEMICAL SYNTHESES USING ALTERNATE REACTION CONDITIONS  

EPA Science Inventory

Microwave (MW) irradiation in conjunction with water as reaction media has proven to be a greener chemical approach for expeditious N-alkylation reactions of amines and hydrazines wherein the reactions under mildly basic conditions afford tertiary amines and double N-alkylation t...

35

Chemical ReactionsChemical Reactions between the Componentsbetween the Components  

E-print Network

products, one the result of an SN2 reaction, the other an E2 reaction. P O O- OH OP O HO OP O O HO + N(C6H.Abundance 700600500400300200100 m/z negative MS 2 610 m/z 256.82 E2 340.83 SN2 609.93 Triphosphate DianionTriphosphate Dianion SN2: Hexyl triphosphate (m/z 341) is produced E2: Triphosphate anion (m/z 257) is produced P O O- OH

Beauchamp, Jack

36

Microfabricated sleeve devices for chemical reactions  

DOEpatents

A silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and non-silicon based materials to provide the thermal properties desired. For example, the chamber may combine a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

Northrup, M. Allen (Berkeley, CA)

2003-01-01

37

Modeling of turbulent chemical reaction  

Microsoft Academic Search

Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent

J.-Y. Chen

1995-01-01

38

Chemical reactions of organic compounds on clay surfaces.  

PubMed Central

Chemical reactions of organic compounds including pesticides at the interlayer and exterior surfaces of clay minerals and with soil organic matter are reviewed. Representative reactions under moderate conditions possibly occurring in natural soils are described. Attempts have been made to clarify the importance of the chemical nature of molecules, their structures and their functional groups, and the Brönsted or Lewis acidity of clay minerals. PMID:2533556

Soma, Y; Soma, M

1989-01-01

39

Conservation-dissipation structure of chemical reaction systems.  

PubMed

In this Brief Report, we show that balanced chemical reaction systems governed by the law of mass action have an elegant conservation-dissipation structure. From this structure a number of important conclusions can be easily deduced. In particular, with the help of this structure we can rigorously justify the classical partial equilibrium approximation in chemical kinetics. PMID:23368081

Yong, Wen-An

2012-12-01

40

Kinetic studies of elementary chemical reactions  

SciTech Connect

This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

1993-12-01

41

Modeling of turbulent chemical reaction  

NASA Technical Reports Server (NTRS)

Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

Chen, J.-Y.

1995-01-01

42

Modeling of turbulent chemical reaction  

NASA Astrophysics Data System (ADS)

Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

Chen, J.-Y.

1995-03-01

43

Chemical Reactions Among Indoor Pollutants  

Microsoft Academic Search

\\u000a Chemistry takes place all around us, regulating the intensity and nature of our exposure to pollutants in water, air and soil.\\u000a In indoor environments, chemistry can significantly alter the composition of the air we breathe. Transformations reduce our\\u000a exposure to reactants and increase our exposure to products. If this reaction takes place on or in a surface, the relative\\u000a exposure

Glenn Morrison

44

Chemical kinetic reaction mechanism for the combustion of propane  

NASA Technical Reports Server (NTRS)

A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

Jachimowski, C. J.

1984-01-01

45

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2013 CFR

... 2013-07-01 false Chemical substances import policy. 707.20 Section...PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS...Restrictions § 707.20 Chemical substances import policy. (a) Scope....

2013-07-01

46

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2011 CFR

... 2011-07-01 false Chemical substances import policy. 707.20 Section...PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS...Restrictions § 707.20 Chemical substances import policy. (a) Scope....

2011-07-01

47

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2010 CFR

... 2010-07-01 false Chemical substances import policy. 707.20 Section...PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS...Restrictions § 707.20 Chemical substances import policy. (a) Scope....

2010-07-01

48

40 CFR 707.20 - Chemical substances import policy.  

Code of Federal Regulations, 2012 CFR

... 2012-07-01 false Chemical substances import policy. 707.20 Section...PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT CHEMICAL IMPORTS AND EXPORTS...Restrictions § 707.20 Chemical substances import policy. (a) Scope....

2012-07-01

49

Quantum chemical approach to estimating the thermodynamics of metabolic reactions.  

PubMed

Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism. PMID:25387603

Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán

2014-01-01

50

Computed potential energy surfaces for chemical reactions  

NASA Technical Reports Server (NTRS)

The objective was to obtain accurate potential energy surfaces (PES's) for a number of reactions which are important in the H/N/O combustion process. The interest in this is centered around the design of the SCRAM jet engine for the National Aerospace Plane (NASP), which was envisioned as an air-breathing hydrogen-burning vehicle capable of reaching velocities as large as Mach 25. Preliminary studies indicated that the supersonic flow in the combustor region of the scram jet engine required accurate reaction rate data for reactions in the H/N/O system, some of which was not readily available from experiment. The most important class of combustion reactions from the standpoint of the NASP project are radical recombinaton reactions, since these reactions result in most of the heat release in the combustion process. Theoretical characterizations of the potential energy surfaces for these reactions are presented and discussed.

Walch, Stephen P.

1990-01-01

51

Mediating chemical reactions using polysaccharides  

NASA Astrophysics Data System (ADS)

We have studied the NaBH4-mediated hydrogenation of select alkenes catalyzed by polysaccharide-stabilized nanoparticles. We compared the catalytic properties of Ni-based nanoparticles or Au/Co-based nanoparticles on the hydrogenation of cinnamic acid, cinnamide, cinnamyl alcohol, and ethyl cinnamate. We evaluated the possibility that the type of stabilizing polysaccharide surrounding the nanoparticle may affect the selectivity towards the alkene compounds that undergo the hydrogenation reaction. We found that the hydrogenation of cinnamide or ethyl cinnamate proceeded readily to 100% completion independent of the type of polysaccharide stabilizing the nanoparticle. However, the extent of the hydrogenation of cinnamyl alcohol and cinnamic acid varied greatly depending on the type of polysaccharide stabilizing the nanoparticle. In the course of these studies, we observed that some polysaccharides by themselves promoted the hydrolysis of ethyl cinnamate. Thus, we have raised the hypothesis that some polysaccharides may act as "esterases" and explored the interaction between select polysaccharides and a variety of ester compounds.

Tyler, Lauren E.

52

Plasmonic smart dust for probing local chemical reactions.  

PubMed

Locally probing chemical reactions or catalytic processes on surfaces under realistic reaction conditions has remained one of the main challenges in materials science and heterogeneous catalysis. Where conventional surface interrogation techniques usually require high-vacuum conditions or ensemble average measurements, plasmonic nanoparticles excel in extreme light focusing and can produce highly confined electromagnetic fields in subwavelength volumes without the need for complex near-field microscopes. Here, we demonstrate an all-optical probing technique based on plasmonic smart dust for monitoring local chemical reactions in real time. The silica shell-isolated gold nanoparticles that form the smart dust can work as strong light concentrators and optically report subtle environmental changes at their pinning sites on the probed surface during reaction processes. As a model system, we investigate the hydrogen dissociation and subsequent uptake trajectory in palladium with both "dust-on-film" and "film-on-dust" platforms. Using time-resolved single particle measurements, we demonstrate that our technique can in situ encode chemical reaction information as optical signals for a variety of surface morphologies. The presented technique offers a unique scheme for real-time, label-free, and high-resolution probing of local reaction kinetics in a plethora of important chemical reactions on surfaces, paving the way toward the development of inexpensive and high-output reaction sensors for real-world applications. PMID:23458121

Tittl, Andreas; Yin, Xinghui; Giessen, Harald; Tian, Xiang-Dong; Tian, Zhong-Qun; Kremers, Christian; Chigrin, Dmitry N; Liu, Na

2013-04-10

53

Formation of ultracold molecules in chemical reactions  

Microsoft Academic Search

We demonstrate that chemical reactions in collisions of high-energy molecular beams can generally produce molecules with zero velocity in the laboratory-fixed frame. Our analysis shows that collisions of beams may simultaneously yield slow reactant molecules and slow products. The reaction products are formed in selected ro-vibrational states and scattered in a specific direction, which can be controlled by tuning the

Timur Tscherbul; Girts Barinovs; Jacek Klos; Roman Krems

2008-01-01

54

Decrease of Entropy and Chemical Reactions  

E-print Network

The chemical reactions are very complex, and include oscillation, condensation, catalyst and self-organization, etc. In these case changes of entropy may increase or decrease. The second law of thermodynamics is based on an isolated system and statistical independence. If fluctuations magnified due to internal interactions exist in the system, entropy will decrease possibly. In chemical reactions there are various internal interactions, so that some ordering processes with decrease of entropy are possible on an isolated system. For example, a simplifying Fokker-Planck equation is solved, and the hysteresis as limit cycle is discussed.

Yi-Fang Chang

2008-07-01

55

Computer Animation of a Chemical Reaction.  

ERIC Educational Resources Information Center

Taking a prototype chemical reaction (molecular hydrogen plus hydrogen atom), constructs an accurate semiempirical, generalized diatomics-in-molecules potential energy surface, calculates motions of these atoms on this surface using REACTS trajectory program, and presents results as moving picture on a microcomputer graphics system. Provides…

Eaker, Charles W.; Jacobs, Edwin L.

1982-01-01

56

Classification of Chemical Reactions: Stages of Expertise  

ERIC Educational Resources Information Center

In this study we explore the strategies that undergraduate and graduate chemistry students use when engaged in classification tasks involving symbolic and microscopic (particulate) representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention when classifying…

Stains, Marilyne; Talanquer, Vicente

2008-01-01

57

A DFT analysis of thermal decomposition reactions important to natural products.  

PubMed

The thermal decomposition reactions of several important natural flavor and fragrance chemicals have been investigated using density functional theory (DFT, B3LYP/6-31G*). Retro-aldol reactions of glucose, fructose, hernandulcin, epihernandulcin, [3]-gingerol, and [4]-isogingerol; retro-carbonyl-ene reactions of isopulegol, lavandulol, isolyratol, and indicumenone; and pyrolytic syn elimination reactions of linalyl acetate, alpha-terpinyl acetate, and bornyl acetate, have been carried out. The calculations indicate activation enthalpies of around 30 kcal/mol for the retro-aldol reactions and for retro-carbonyl-ene reactions, comparable to pericyclic reactions such as the Cope rearrangement and electrocyclic reactions, and therefore important reactions at elevated temperatures (e.g., boiling aqueous solutions, gas-chromatograph injection ports). Activation enthalpies for pyrolytic eliminations are around 40 kcal/mol and are unlikely to occur during extraction or GC analysis. PMID:20734926

Setzer, William N

2010-07-01

58

Computed potential energy surfaces for chemical reactions  

NASA Technical Reports Server (NTRS)

A new global potential energy surface (PES) is being generated for O(P-3) + H2 yields OH + H. This surface is being fit using the rotated Morse oscillator method, which was used to fit the previous POL-CI surface. The new surface is expected to be more accurate and also includes a much more complete sampling of bent geometries. A new study has been undertaken of the reaction N + O2 yields NO + O. The new studies have focused on the region of the surface near a possible minimum corresponding to the peroxy form of NOO. A large portion of the PES for this second reaction has been mapped out. Since state to state cross sections for the reaction are important in the chemistry of high temperature air, these studies will probably be extended to permit generation of a new global potential for reaction.

Walch, Stephen P.; Levin, Eugene

1993-01-01

59

Chemical Reaction due to Stronger Ramachandran Interaction  

E-print Network

The origin of a chemical reaction between two reactant atoms is associated to the activation energy, with the assumption that, high-energy collisions between these atoms, are the ones that overcome the activation energy. Here, we (i) show that a stronger attractive van der Waals (vdW) and electron-ion Coulomb interactions between two polarized atoms are responsible to initiate a chemical reaction, either before or after the collision. We derive this stronger vdW attraction formula exactly using the quasi one-dimensional Drude model within the ionization energy theory and the energy-level spacing renormalization group method. Along the way, we (ii) expose the precise physical mechanism responsible for the existence of a stronger vdW interaction for both long and short distances, and also show how to technically avoid the electron-electron Coulomb repulsion between polarized electrons from these two reactant atoms. Finally, we properly and correctly associate the existence of this stronger attraction to Ramachandran's 'normal limits' (distance shorter than what is allowed by the standard vdW bond) between chemically nonbonded atoms.

Andrew Das Arulsamy

2011-10-15

60

The role of chemical reactions in the Chernobyl accident  

SciTech Connect

It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity, apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe-235 on the second day after the explosion led to a reactor power of 80-110 MW. Owing to this power, the chemical reactions of reduction of uranium, plutonium, and other metals at a temperature of about 2000 Degree-Sign C occurred in the core. The yield of fission products thus sharply increased. Uranium and other metals flew down in the bottom water communications and rooms. After reduction of the uranium and its separation from the graphite, the chain reaction stopped, the temperature of the core decreased, and the activity yield stopped.

Grishanin, E. I., E-mail: egrishanin@orexovo.net [Russian Research Center Kurchatov Institute (Russian Federation)

2010-12-15

61

The role of chemical reactions in the Chernobyl accident  

NASA Astrophysics Data System (ADS)

It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity, apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe-235 on the second day after the explosion led to a reactor power of 80-110 MW. Owing to this power, the chemical reactions of reduction of uranium, plutonium, and other metals at a temperature of about 2000°C occurred in the core. The yield of fission products thus sharply increased. Uranium and other metals flew down in the bottom water communications and rooms. After reduction of the uranium and its separation from the graphite, the chain reaction stopped, the temperature of the core decreased, and the activity yield stopped.

Grishanin, E. I.

2010-12-01

62

Multiscale stochastic simulations of chemical reactions with regulated scale separation  

SciTech Connect

We present a coupling of multiscale frameworks with accelerated stochastic simulation algorithms for systems of chemical reactions with disparate propensities. The algorithms regulate the propensities of the fast and slow reactions of the system, using alternating micro and macro sub-steps simulated with accelerated algorithms such as ? and R-leaping. The proposed algorithms are shown to provide significant speedups in simulations of stiff systems of chemical reactions with a trade-off in accuracy as controlled by a regulating parameter. More importantly, the error of the methods exhibits a cutoff phenomenon that allows for optimal parameter choices. Numerical experiments demonstrate that hybrid algorithms involving accelerated stochastic simulations can be, in certain cases, more accurate while faster, than their corresponding stochastic simulation algorithm counterparts.

Koumoutsakos, Petros, E-mail: petros@ethz.ch [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland); Feigelman, Justin [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)] [Chair of Computational Science, Clausiusstrasse 33, ETH Zurich, CH-8092 (Switzerland)

2013-07-01

63

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air  

Microsoft Academic Search

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities

J. H. Park; E. Pfender; C. H. Chang

2000-01-01

64

Quantum dynamics of fast chemical reactions  

SciTech Connect

The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

Light, J.C. [Univ. of Chicago, IL (United States)

1993-12-01

65

Supersonic molecular beam experiments on surface chemical reactions.  

PubMed

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. PMID:25044656

Okada, Michio

2014-10-01

66

Computed Potential Energy Surfaces for Chemical Reactions  

NASA Technical Reports Server (NTRS)

A manuscript describing the calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction, which were described in the last progress report, has been accepted for publication in J. Chem. Phys., and a copy of the manuscript is included in the appendix. The production of (1)CH2 in this reaction is important in hydrocarbon combustion since (1)CH2 is highly reactive and would be expected to insert into N2, possibly leading to a new source for prompt NO(x) (vide infra). During the last six months new calculations have been carried out for the NH2 + NO system, which is important in the thermal de-NO(x) process.

Heinemann, K.; Walch, Stephen P.; Levin, Eugene

1993-01-01

67

Chemical reaction fouling model for single-phase heat transfer  

SciTech Connect

A fouling model was developed on the premise that the chemical reaction for generation of precursor can take place in the bulk fluid, in the thermalboundary layer, or at the fluid/wall interface, depending upon the interactive effects of flu id dynamics, heat and mass transfer, and the controlling chemical reaction. The analysis was used to examine the experimental data for fouling deposition of polyperoxides produced by autoxidation of indene in kerosene. The effects of fluid and wall temperatures for two flow geometries were analyzed. The results showed that the relative effects of physical parameters on the fouling rate would differ for the three fouling mechanisms; therefore, it is important to identify the controlling mechanism in applying the closed-flow-loop data to industrial conditions.

Panchal, C.B. [Argonne National Lab., IL (United States); Watkinson, A.P. [British Columbia Univ., Vancouver, BC (Canada)

1993-08-01

68

Silicon-based sleeve devices for chemical reactions  

DOEpatents

A silicon-based sleeve type chemical reaction chamber that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis.

Northrup, M. Allen (Berkeley, CA); Mariella, Jr., Raymond P. (Danville, CA); Carrano, Anthony V. (Livermore, CA); Balch, Joseph W. (Livermore, CA)

1996-01-01

69

Silicon-based sleeve devices for chemical reactions  

DOEpatents

A silicon-based sleeve type chemical reaction chamber is described that combines heaters, such as doped polysilicon for heating, and bulk silicon for convection cooling. The reaction chamber combines a critical ratio of silicon and silicon nitride to the volume of material to be heated (e.g., a liquid) in order to provide uniform heating, yet low power requirements. The reaction chamber will also allow the introduction of a secondary tube (e.g., plastic) into the reaction sleeve that contains the reaction mixture thereby alleviating any potential materials incompatibility issues. The reaction chamber may be utilized in any chemical reaction system for synthesis or processing of organic, inorganic, or biochemical reactions, such as the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction, which are examples of a synthetic, thermal-cycling-based reaction. The reaction chamber may also be used in synthesis instruments, particularly those for DNA amplification and synthesis. 32 figs.

Northrup, M.A.; Mariella, R.P. Jr.; Carrano, A.V.; Balch, J.W.

1996-12-31

70

Plasmon-assisted chemical reactions revealed by high-vacuum tip-enhanced Raman spectroscopy  

NASA Astrophysics Data System (ADS)

Tip-enhanced Raman spectroscopy (TERS) is the technique that combines the nanoscale spatial resolution of a scanning probe microscope and the highly sensitive Raman spectroscopy enhanced by the surface plasmons. It is suitable for chemical analysis at nanometer scale. Recently, TERS exhibited powerful potential in analyzing the chemical reactions at nanoscale. The high sensitivity and spatial resolution of TERS enable us to learn the reaction processes more clearly. More importantly, the chemical reaction in TERS is assisted by surface plasmons, which provides us an optical method to manipulate the chemical reactions at nanoscale. Here using our home-built high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup, we successfully observed the plasmon-assisted molecule dimerization and dissociation reactions. In HV-TERS system, under laser illumination, 4-nitrobenzenethiol (4NBT) molecules can be dimerized to p,p'-dimercaptoazobenzene (DMAB), and dissociation reaction occurs for malachite green (MG) molecules. Using our HV-TERS setup, the dynamic processes of the reactions are clearly revealed. The chemical reactions can be manipulated by controlling the plasmon intensity through changing the power of the incident laser, the tunneling current and the bias voltage. We also investigated the role of plasmonic thermal effect in the reactions by measuring both the Stokes and anti- Stokes Raman peaks. Our findings extend the applications of TERS, which can help to study the chemical reactions and understand the dynamic processes at single molecular level, and even design molecules by the plasmon-assisted chemical reactions.

Lu, Shuaicheng; Sheng, Shaoxiang; Zhang, Zhenglong; Xu, Hongxing; Zheng, Hairong

2014-08-01

71

A Review on Chemical Reactions of Solid Lubricants During Friction  

Microsoft Academic Search

A historical background on chemical reactions between solids, in which the chemical activation energy is generated by mechanical forces, is presented and a literature review on “mechano-chemical” or “tribo-chemical” reactions occurring between solid lubricants such as MoS2 and Zn2P2O7 and metal surfaces is given. According to the work reviewed, MoS2 reacts with steel surfaces under boundary friction conditions forming FeS

J. Gansheimer

1972-01-01

72

Heterogeneous chemical reactions: Preparation of monodisperse latexes  

NASA Technical Reports Server (NTRS)

It is demonstrated that a photoinitiated emulsion polymerization can be carried out to a significant conversion in a SPAR rocket prototype polymerization vessel within the six minutes allowed for the experiment. The percentage of conversion was determined by both dilatometry and gravimetric methods with good agreement. The experimental results lead to the following conclusions: (1) emulsion polymerizations can be carried out to conversions as high as 75%, using a stable micellized styrene-SLS system plus photoinitiator; (2) dilatometry can be used to accurately determine both the rate and conversion of polymerization; (3) thermal expansion due to the light source and heat of reaction is small and can be corrected for if necessary; (4) although seeded emulsion polymerizations are unfavorable in photoinitiation, as opposed to chemical initiation, polymerizations can be carried out to at least 15% conversion using 7940A seed particles, with 0.05% solids; and (5) photoinitiation should be used to initiate polymerization in the SPAR rocket experiments because of the mechanical simplicity of the experiment.

Vanderhoff, J. W.; Micale, F. J.; El-Aasser, M. S.; Sterk, A. A.; Bethke, G. W.

1977-01-01

73

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions Shannon D and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird useful, and the gas dynamics of many systems is more easily predicted and understood by using Monte Carlo

Anderson, James B.

74

Advanced Chemical Heat Pumps Using Liquid-Vapor Reactions  

E-print Network

-vapor chemical reactions. . ~ Heat pumps using liquid-vapor reactions f (items 1 and 5, above) are the subjects of this paper. Configurations discussed are: r , ! 1. Electric drive 2. Temperature amplifier (TA) using Rankine heat engine and liquid...-vapor reaction heat pump 3. Heat amplifier (HA) using liquid-vapor ' " reaction heat engine and reverse Rankine heat pump 4. HA and TA in which both heat engine and heat pump use liquid-vapor reactions. Thermodynamic requirements for working fluids...

Kirol, L.

75

Investigating Factors Influencing Rates of Chemical Reactions  

NSDL National Science Digital Library

This activity is a lab investigation in which students observe the rate of generation of hydrogen gas from a reaction, and then modify the procedure to compare another variable affecting the rate of this reaction.

Derickson, Paula

76

Deterministic Function Computation with Chemical Reaction Networks*  

PubMed Central

Chemical reaction networks (CRNs) formally model chemistry in a well-mixed solution. CRNs are widely used to describe information processing occurring in natural cellular regulatory networks, and with upcoming advances in synthetic biology, CRNs are a promising language for the design of artificial molecular control circuitry. Nonetheless, despite the widespread use of CRNs in the natural sciences, the range of computational behaviors exhibited by CRNs is not well understood. CRNs have been shown to be efficiently Turing-universal (i.e., able to simulate arbitrary algorithms) when allowing for a small probability of error. CRNs that are guaranteed to converge on a correct answer, on the other hand, have been shown to decide only the semilinear predicates (a multi-dimensional generalization of “eventually periodic” sets). We introduce the notion of function, rather than predicate, computation by representing the output of a function f : ?k ? ?l by a count of some molecular species, i.e., if the CRN starts with x1, …, xk molecules of some “input” species X1, …, Xk, the CRN is guaranteed to converge to having f(x1, …, xk) molecules of the “output” species Y1, …, Yl. We show that a function f : ?k ? ?l is deterministically computed by a CRN if and only if its graph {(x, y) ? ?k × ?l ? f(x) = y} is a semilinear set. Finally, we show that each semilinear function f (a function whose graph is a semilinear set) can be computed by a CRN on input x in expected time O(polylog ?x?1).

Chen, Ho-Lin; Doty, David; Soloveichik, David

2013-01-01

77

Incidents of chemical reactions in cell equipment  

SciTech Connect

Strongly exothermic reactions can occur between equipment structural components and process gases under certain accident conditions in the diffusion enrichment cascades. This paper describes the conditions required for initiation of these reactions, and describes the range of such reactions experienced over nearly 50 years of equipment operation in the US uranium enrichment program. Factors are cited which can promote or limit the destructive extent of these reactions, and process operations are described which are designed to control the reactions to minimize equipment damage, downtime, and the possibility of material releases.

Baldwin, N.M.; Barlow, C.R. [Uranium Enrichment Organization, Oak Ridge, TN (United States)

1991-12-31

78

Single-collision studies of energy transfer and chemical reaction  

SciTech Connect

The research focus in this group is state-to-state dynamics of reaction and energy transfer in collisions of free radicals such as H, OH, and CH{sub 3} with H{sub 2}, alkanes, alcohols and other hydrogen-containing molecules. The motivation for the work is the desire to provide a detailed understanding of the chemical dynamics of prototype reactions that are important in the production and utilization of energy sources, most importantly in combustion. The work is primarily experimental, but with an important and growing theoretical/computational component. The focus of this research program is now on reactions in which at least one of the reactants and one of the products is polyatomic. The objective is to determine how the high dimensionality of the reactants and products differentiates such reactions from atom + diatom reactions of the same kinematics and energetics. The experiments use highly time-resolved laser spectroscopic methods to prepare reactant states and analyze the states of the products on a single-collision time scale. The primary spectroscopic tool for product state analysis is coherent anti-Stokes Raman scattering (CARS) spectroscopy. CARS is used because of its generality and because the extraction of quantum state populations from CARS spectra is straightforward. The combination of the generality and easy analysis of CARS makes possible absolute cross section measurements (both state-to-state and total), a particularly valuable capability for characterizing reactive and inelastic collisions. Reactant free radicals are produced by laser photolysis of appropriate precursors. For reactant vibrational excitation stimulated Raman techniques are being developed and implemented.

Valentini, J.J. [Columbia Univ., New York, NY (United States)

1993-12-01

79

Mechano-chemical coupling in Belousov-Zhabotinskii reactions.  

PubMed

Mechano-chemical coupling has been recently recognised as an important effect in various systems as chemical reactivity can be controlled through an applied mechanical loading. Namely, Belousov-Zhabotinskii reactions in polymer gels exhibit self-sustained oscillations and have been identified to be reasonably controllable and definable to the extent that they can be harnessed to perform mechanical work at specific locations. In this paper, we use our theoretical work of nonlinear mechano-chemical coupling and investigate the possibility of providing an explanation of phenomena found in experimental research by means of this theory. We show that mechanotransduction occurs as a response to both static and dynamic mechanical stimulation, e.g., volume change and its rate, as observed experimentally and discuss the difference of their effects on oscillations. Plausible values of the quasi-stoichiometric parameter f of Oregonator model are estimated together with its dependence on mechanical stimulation. An increase in static loading, e.g., pressure, is predicted to have stimulatory effect whereas dynamic loading, e.g., rate of volume change, is predicted to be stimulatory only up to a certain threshold. Further, we offer a physically consistent explanation of the observed phenomena why some Belousov-Zhabotinskii gels require an additional mechanical stimulation to show emergence of oscillation or why "revival" of oscillations in Belousov-Zhabotinskii reactions is possible together with indications for further experimental setups. PMID:24697427

Klika, Václav; Grmela, Miroslav

2014-03-28

80

Chemical Looping Combustion Reactions and Systems  

SciTech Connect

Chemical Looping Combustion (CLC) is one promising fuel-combustion technology, which can facilitate economic CO2 capture in coal-fired power plants. It employs the oxidation/reduction characteristics of a metal, or oxygen carrier, and its oxide, the oxidizing gas (typically air) and the fuel source may be kept separate. This work focused on two classes of oxygen carrier, one that merely undergoes a change in oxidation state, such as Fe3O4/Fe2O3 and one that is converted from its higher to its lower oxidation state by the release of oxygen on heating, i.e., CuO/Cu2O. This topical report discusses the results of four complementary efforts: (1) the development of process and economic models to optimize important design considerations, such as oxygen carrier circulation rate, temperature, residence time; (2) the development of high-performance simulation capabilities for fluidized beds and the collection, parameter identification, and preliminary verification/uncertainty quantification (3) the exploration of operating characteristics in the laboratory-scale bubbling bed reactor, with a focus on the oxygen carrier performance, including reactivity, oxygen carrying capacity, attrition resistance, resistance to deactivation, cost and availability (4) the identification of mechanisms and rates for the copper, cuprous oxide, and cupric oxide system using thermogravimetric analysis.

Sarofim, Adel; Lighty, JoAnn; Smith, Philip; Whitty, Kevin; Eyring, Edward; Sahir, Asad; Alvarez, Milo; Hradisky, Michael; Clayton, Chris; Konya, Gabor; Baracki, Richard; Kelly, Kerry

2011-07-01

81

Systems of Chemical Equations as Reasonable Reaction Mechanisms  

NASA Astrophysics Data System (ADS)

This paper demonstrates that chemical equations may be operated like a kind of LEGO game, with construction of the systems of chemical equations. In my teaching experience, these systems of chemical equations are able to help students to understand the reaction routes. Six general principles of creating the systems are formulated. Three examples from inorganic chemistry are considered and discussed in detail.

Dorozhkin, Sergey V.

2001-07-01

82

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance  

NASA Technical Reports Server (NTRS)

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemistry parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory.

Molina, Mario J.

1997-01-01

83

CHEMICAL TAILORING OF TEICOPLANIN WITH SITE-SELECTIVE REACTIONS  

PubMed Central

Semi-synthesis of natural product derivatives combines the power of fermentation with orthogonal chemical reactions. Yet, chemical modification of complex structures represents an unmet challenge, as poor selectivity often undermines efficiency. The complex antibiotic teicoplanin eradicates bacterial infections. However, as resistance emerges, the demand for improved analogs grows. We have discovered chemical reactions that achieve site-selective alteration of teicoplanin. Utilizing peptide-based additives that alter reaction selectivities, certain bromo-teicoplanins are accessible. These new compounds are also scaffolds for selective cross-coupling reactions, enabling further molecular diversification. These studies enable two-step access to glycopeptide analogs not available through either biosynthesis or rapid total chemical synthesis alone. The new compounds exhibit a spectrum of activities, revealing that selective chemical alteration of teicoplanin may lead to analogs with attenuated or enhanced antibacterial properties, in particular against vancomycin and teicoplanin resistance strains. PMID:23692563

Pathak, Tejas P.; Miller, Scott J.

2013-01-01

84

Chemical tailoring of teicoplanin with site-selective reactions.  

PubMed

Semisynthesis of natural product derivatives combines the power of fermentation with orthogonal chemical reactions. Yet, chemical modification of complex structures represents an unmet challenge, as poor selectivity often undermines efficiency. The complex antibiotic teicoplanin eradicates bacterial infections. However, as resistance emerges, the demand for improved analogues grows. We have discovered chemical reactions that achieve site-selective alteration of teicoplanin. Utilizing peptide-based additives that alter reaction selectivities, certain bromo-teicoplanins are accessible. These new compounds are also scaffolds for selective cross-coupling reactions, enabling further molecular diversification. These studies enable two-step access to glycopeptide analogues not available through either biosynthesis or rapid total chemical synthesis alone. The new compounds exhibit a spectrum of activities, revealing that selective chemical alteration of teicoplanin may lead to analogues with attenuated or enhanced antibacterial properties, in particular against vancomycin- and teicoplanin-resistant strains. PMID:23692563

Pathak, Tejas P; Miller, Scott J

2013-06-01

85

FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS  

EPA Science Inventory

The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

86

The How and Why of Chemical Reactions  

ERIC Educational Resources Information Center

Presents a discussion of some of the fundamental concepts in thermodynamics and quantum mechanics including entropy, enthalpy, free energy, the partition function, chemical kinetics, transition state theory, the making and breaking of chemical bonds, electronegativity, ion sizes, intermolecular energies and of their role in explaining the nature…

Schubert, Leo

1970-01-01

87

Kinetics of Chemical Reactions in Flames  

NASA Technical Reports Server (NTRS)

In part I of the paper the theory of flame propagation is developed along the lines followed by Frank-Kamenetsky and one of the writers. The development of chain processes in flames is considered. A basis is given for the application of the method of stationary concentrations to reactions in flames; reactions with branching chains are analyzed. The case of a diffusion coefficient different from the coefficient of temperature conductivity is considered.

Zeldovich, Y.; Semenov, N.

1946-01-01

88

Application of Reversible Chemical Reactions for Temperature Amplification  

E-print Network

temperature thermal energy, mechanical and absorption type heat pumps have been proposed and developed so far. This paper addresses itself to the concept of a heat reaction chemical heat pump (HRCHP). The HRCHP concept is aimed to upgrade low temperature...

Ally, M. R.; Rebello, W. J.; Suciu, D. F.

89

Log-domain circuit models of chemical reactions  

E-print Network

We exploit the detailed similarities between electronics and chemistry to develop efficient, scalable bipolar or subthreshold log-domain circuits that are dynamically equivalent to networks of chemical reactions. Our ...

Mandal, Soumyajit

90

Design and development of chemical ontologies for reaction representation.  

PubMed

This paper describes the development of chemical ontologies applied to the representation of organic chemical reactions. The ontologies are built using the methodology known as methontology. The hierarchically structured set of terms describing the subdomains, namely, organic reactions, organic compounds, and reagents, are constructed into individual ontologies. The ontologies consist of about 200 concepts and around 125 individuals. A set of binary relations is defined in order to integrate the ontologies with applications. The ontologies are implemented as an XML application with a set of vocabulary describing the domain knowledge. This paper also features an easy-to-use chemical ontological support system (COSS) intended to represent organic chemical reactions automatically. As a model application, the automatic representation of aliphatic nucleophilic substitution reactions is demonstrated using COSS. The paper also describes a keyword-based search system whose functionality is backed with COSS. PMID:17125179

Sankar, Punnaivanam; Aghila, Gnanasekaran

2006-01-01

91

CHEMICAL REACTIONS SIMULATED BY GROUND-WATER-QUALITY MODELS.  

USGS Publications Warehouse

Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

Grove, David, B.; Stollenwerk, Kenneth, G.

1987-01-01

92

Collisions, Chemical Reactions, and Transport Chemistry 223  

E-print Network

. Effusion, Wall Collisions, and Surface Reactions In the previous section, we found the parameter b application of this expression is in effusion though a pinhole. If there is a hole of area A in the surface will escape more slowly (with a 1/mass dependence); hence, effusion through a pinhole is a simple way in which

Ronis, David M.

93

Brownian dynamics simulation of a chemical reaction in solution  

Microsoft Academic Search

We present a study, using the brownian dynamics simulation technique, of a simple model of a chemical reaction in solution. The model consists of the transfer of a particle between two substrate species in a reaction complex which interacts with its surroundings through frictional effects and random force terms. We pay particular attention to the regime in which both the

M. P. Allen

1980-01-01

94

Cu-free click cycloaddition reactions in chemical biology†  

PubMed Central

Bioorthogonal chemical reactions are paving the way for new innovations in biology. These reactions possess extreme selectivity and biocompatibility, such that their participating reagents can form covalent bonds within richly functionalized biological systems—in some cases, living organisms. This tutorial review will summarize the history of this emerging field, as well as recent progress in the development and application of bioorthogonal copper-free click cycloaddition reactions. PMID:20349533

Jewett, John C.

2010-01-01

95

Polymer Reaction Engineering Laboratory Chemical and Biomolecular Engineering  

E-print Network

the instructions up to the step 9. 1. Main power switch on, blower switch off, pressure control switchPolymer Reaction Engineering Laboratory Chemical and Biomolecular Engineering University for chemical purity. The second type of daily activity involves controlling the position of the gloves

Choi, Kyu Yong

96

LIGAND: Database of Chemical Compounds and Reactions in Biological Pathways  

NSDL National Science Digital Library

The Institute for Chemical Research at Kyoto University provides this frequently updated and well-documented database of enzyme reactions. With more than 9,300 entries, the LIGAND Chemical Database includes over 3,700 entries for enzymes (the Enzyme Reaction Database) and 5,600 entries for compounds (Chemical Compound Database). The database is searchable by keyword using DBGET (which supports numerous other databases and gene catalogs as well) and is accompanied by clear instructions. The LIGAND database, updated weekly, may be downloaded via anonymous FTP.

97

Laser cutting with chemical reaction assist  

DOEpatents

A method for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation.

Gettemy, Donald J. (Los Alamos, NM)

1992-01-01

98

Laser cutting with chemical reaction assist  

DOEpatents

A method is described for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation. 1 figure.

Gettemy, D.J.

1992-11-17

99

Laser cutting with chemical reaction assist  

SciTech Connect

This invention is comprised of a method for cutting with a laser beam where an oxygen-hydrocarbon reaction is used to provide auxiliary energy to a metal workpiece to supplement the energy supplied by the laser. Oxygen is supplied to the laser focus point on the workpiece by a nozzle through which the laser beam also passes. A liquid hydrocarbon is supplied by coating the workpiece along the cutting path with the hydrocarbon prior to laser irradiation or by spraying a stream of hydrocarbon through a nozzle aimed at a point on the cutting path which is just ahead of the focus point during irradiation.

Gettemy, D.J.

1991-04-08

100

Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.  

PubMed

Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps. PMID:24963600

Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

2014-01-01

101

Sequential Voronoi diagram calculations using simple chemical reactions  

E-print Network

In our recent paper [de Lacy Costello et al. 2010] we described the formation of complex tessellations of the plane arising from the various reactions of metal salts with potassium ferricyanide and ferrocyanide loaded gels. In addition to producing colourful tessellations these reactions are naturally computing generalised Voronoi diagrams of the plane. The reactions reported previously were capable of the calculation of three distinct Voronoi diagrams of the plane. As diffusion coupled with a chemical reaction is responsible for the calculation then this is achieved in parallel. Thus an increase in the complexity of the data input does not utilise additional computational resource. Additional benefits of these chemical reactions is that a permanent record of the Voronoi diagram calculation (in the form of precipitate free bisectors) is achieved, so there is no requirement for further processing to extract the calculation results. Previously it was assumed that the permanence of the results was also a potenti...

Costello, Ben de Lacy; Adamatzky, Andy

2012-01-01

102

The effect of carbon nanotubes on chiral chemical reactions  

NASA Astrophysics Data System (ADS)

The intrinsic helicity of carbon nanotubes influences the formation of chiral molecules in chemical reactions. A racemic mixture of P and M enantiomers of nanotubes affects the enantiomeric excess of the products of the autocatalytic Soai reaction proportional to the amount of nanotubes added in the reaction mixture. An intermediate complex formed between the nanotube and the organometallic reagent is essential and explains the observed correlation between the enantiomeric distribution of products and the curvature of the carbon nanostructure. This Letter establishes a key mechanism for harnessing the helicity of nanoscale carbon surfaces for preparative organic reactions.

Rance, Graham A.; Miners, Scott A.; Chamberlain, Thomas W.; Khlobystov, Andrei N.

2013-02-01

103

Laboratory studies of sticking coefficients and heterogeneous reactions important in the stratosphere  

NASA Technical Reports Server (NTRS)

The discovery of ozone depletion during spring in the Antarctic stratosphere has received wide spread attention. Both meteorological and chemical mechanisms have been used in attempts to explain this observation. The chemical theory focused on the chlorofluoromethanes released into the atmosphere. However, gas-phase, homogeneous reactions alone in the model can not adequately explain such a depletion. Heterogeneous reactions on ice surfaces could be important in the Antarctic stratosphere. These reactions are thought to convert ClONO2 and N2O5 into HNO3 in the solid phase while Cl2, HOCl, and ClNO2 are released into the stratosphere as gas-phase products. The photolysis of Cl2, HOCl, and ClNO2, then produces active chlorine which subsequently removes ozone through several catalytic cycles, including the Cl2O2 mechanism. The polar stratospheric clouds are thought to consist of mixtures of water ice, nitric acid, and sulfuric acid. Condensation of HCl onto the PSC's could provide active surfaces for heterogeneous reactions.

Leu, Ming-Taun

1988-01-01

104

Automatic NMR-based identification of chemical reaction types in mixtures of co-occurring reactions.  

PubMed

The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the (1)H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the (1)H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of the molecules in the mixtures. PMID:24551112

Latino, Diogo A R S; Aires-de-Sousa, João

2014-01-01

105

Modeling Chemical Reactions on Metal Oxide Surfaces  

NASA Astrophysics Data System (ADS)

Photocatalytic conversion of carbon dioxide to methanol has been observed at titanium dioxide interfaces, but the detailed mechanisms are unknown. Computer simulations can prove valuable in elucidating the mechanisms and aid in improving the efficiency. Two major computational strategies for treating such systems are slab and cluster models. The present work uses both periodic slab and embedded cluster models to elucidate the important factors in developing an embedding scheme that properly treats the system and allows the treatment of excited electronic states. Ground state adsorption energies are calculated for a variety of basis sets, cluster sizes, electronic structure methods and embedding schemes to demonstrate convergence with respect to all of these variables. Detailed comparisons of the electrostatic potential obtained from periodic and embedded cluster models are presented to clarify the importance of various effects in the embedding scheme.

Liu, Haitao; Falcetta, Michael; Jordan, Kenneth

2009-03-01

106

STM CONTROL OF CHEMICAL REACTIONS: Single-Molecule Synthesis  

NASA Astrophysics Data System (ADS)

The fascinating advances in single atom/molecule manipulation with a scanning tunneling microscope (STM) tip allow scientists to fabricate atomic-scale structures or to probe chemical and physical properties of matters at an atomic level. Owing to these advances, it has become possible for the basic chemical reaction steps, such as dissociation, diffusion, adsorption, readsorption, and bond-formation processes, to be performed by using the STM tip. Complete sequences of chemical reactions are able to induce at a single-molecule level. New molecules can be constructed from the basic molecular building blocks on a one-molecule-at-a-time basis by using a variety of STM manipulation schemes in a systematic step-by-step manner. These achievements open up entirely new opportunities in nanochemistry and nanochemical technology. In this review, various STM manipulation techniques useful in the single-molecule reaction process are reviewed, and their impact on the future of nanoscience and technology are discussed.

Hla, Saw-Wai; Rieder, Karl-Heinz

2003-10-01

107

International chemical identifier for reactions (RInChI)  

PubMed Central

The IUPAC International Chemical Identifier (InChI) provides a method to generate a unique text descriptor of molecular structures. Building on this work, we report a process to generate a unique text descriptor for reactions, RInChI. By carefully selecting the information that is included and by ordering the data carefully, different scientists studying the same reaction should produce the same RInChI. If differences arise, these are most likely the minor layers of the InChI, and so may be readily handled. RInChI provides a concise description of the key data in a chemical reaction, and will help enable the rapid searching and analysis of reaction databases. PMID:24152584

2013-01-01

108

Gas-phase reactions of halogen species of atmospheric importance  

NASA Astrophysics Data System (ADS)

A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen-containing molecules and between NO3 radicals and the iodine species I2 and I. These experiments have shown that: (1) the reaction of methyl iodide with OH accounts for approximately 2 percent of the removal of CH3I from the troposphere as compared with photolysis; (2) abstraction of I-atoms from a C-I bond by OH is probable in the gas-phase; (3) the halogen-containing anaesthetic substances halothane CF3CClBrH, enflurane CF2HOCF2CFClH, isoflurane CF2HOCClHCF3 and sevoflurane (CF3)2CHOCFH2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross-sections of the compounds in the spectral region 800-1200 cm(exp -1) were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl3 for each compound. The study of the reactions between OH and CF3CFBrH and CF2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of reaction, the rate constant of which was found to be (1.5 +/- 0.5) x 10(exp -12)/cu cm/molecule/s. The reaction between I and NO3 was found to occur at a rate of about 60 percent of the hard-sphere collision frequency for the two species. The rate constant for reaction between I and NO3 was found to be (4.5 +/- 1.9) x 10(exp -10)/cu cm/molecule/s. An upper limit for the heat of formation of IONO2 of (21 +/- 3) kJmol(exp -1) was also derived.

Heard, Anne C.

109

Rapid chemical reaction workup based on a rigid solvent extraction.  

PubMed

The conventional chemical reaction workup based on liquid-liquid extraction is a time- and labor-consuming practice. We have developed a substantially faster technique for the routine workup that relies on a porous organic polymer (Porelite) supported solvent phase to extract organic products from an aqueous reaction mixture. We call this process rigid solvent extraction. Using this technique, the tedious liquid-liquid extraction can be replaced by a simple filtration, making parallel operation and automation feasible. PMID:25296390

Xu, Bo; Hammond, Gerald B

2014-10-17

110

Dynamic control and information processing in chemical reaction systems by tuning self-organization behavior  

NASA Astrophysics Data System (ADS)

Specific external control of chemical reaction systems and both dynamic control and signal processing as central functions in biochemical reaction systems are important issues of modern nonlinear science. For example nonlinear input-output behavior and its regulation are crucial for the maintainance of the life process that requires extensive communication between cells and their environment. An important question is how the dynamical behavior of biochemical systems is controlled and how they process information transmitted by incoming signals. But also from a general point of view external forcing of complex chemical reaction processes is important in many application areas ranging from chemical engineering to biomedicine. In order to study such control issues numerically, here, we choose a well characterized chemical system, the CO oxidation on Pt(110), which is interesting per se as an externally forced chemical oscillator model. We show numerically that tuning of temporal self-organization by input signals in this simple nonlinear chemical reaction exhibiting oscillatory behavior can in principle be exploited for both specific external control of dynamical system behavior and processing of complex information.

Lebiedz, Dirk; Brandt-Pollmann, Ulrich

2004-09-01

111

Waste dissolution with chemical reaction, diffusion and advection  

SciTech Connect

This paper extends the mass-transfer analysis to include the effect of advective transport in predicting the steady-state dissolution rate, with a chemical-reaction-rate boundary condition at the surface of a waste form of arbitrary shape. This new theory provides an analytic means of predicting the ground-water velocities at which dissolution rate in a geologic environment will be governed entirely to the chemical reaction rate. As an illustration, we consider the steady-state potential flow of ground water in porous rock surrounding a spherical waste solid. 3 refs., 2 figs.

Chambre, P.L.; Kang, C.H.; Lee, W.W.L.; Pigford, T.H.

1987-06-01

112

Simulation of chemical reaction dynamics on an NMR quantum computer  

E-print Network

Quantum simulation can beat current classical computers with minimally a few tens of qubits and will likely become the first practical use of a quantum computer. One promising application of quantum simulation is to attack challenging quantum chemistry problems. Here we report an experimental demonstration that a small nuclear-magnetic-resonance (NMR) quantum computer is already able to simulate the dynamics of a prototype chemical reaction. The experimental results agree well with classical simulations. We conclude that the quantum simulation of chemical reaction dynamics not computable on current classical computers is feasible in the near future.

Dawei Lu; Nanyang Xu; Ruixue Xu; Hongwei Chen; Jiangbin Gong; Xinhua Peng; Jiangfeng Du

2011-05-21

113

Detailed Chemical Kinetic Reaction Mechanisms for Incineration of Organophosphorus and Fluoro-Organophosphorus Compounds  

SciTech Connect

A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a six-center molecular elimination reaction producing propene.

Glaude, P A; Melius, C; Pitz, W J; Westbrook, C K

2001-12-13

114

CHARACTERIZATION OF CHEMICALLY MODIFIED HYPERTHERMOPHILIC ENZYMES FOR CHEMICAL SYNTHESES AND BIOREMEDIATION REACTIONS  

EPA Science Inventory

Research developments in the area of biocatalysis in organic solvents are expected to greatly expand the role of bioprocessing in chemical synthesis, fuel processing, and bioremediation technologies. Many biological transformation reactions of interest to DOE site remediation inv...

115

Modeling Second-Order Chemical Reactions using Cellular Automata  

NASA Astrophysics Data System (ADS)

Cellular automata (CA) are discrete, agent-based, dynamic, iterated, mathematical computational models used to describe complex physical, biological, and chemical systems. Unlike the more computationally demanding molecular dynamics and Monte Carlo approaches, which use "force fields" to model molecular interactions, CA models employ a set of local rules. The traditional approach for modeling chemical reactions is to solve a set of simultaneous differential rate equations to give deterministic outcomes. CA models yield statistical outcomes for a finite number of ingredients. The deterministic solutions appear as limiting cases for conditions such as a large number of ingredients or a finite number of ingredients and many trials. Here we present a 2-dimensional, probabilistic CA model of a second-order gas phase reaction A + B ? C, using a MATLAB basis. Beginning with a random distribution of ingredients A and B, formation of C emerges as the system evolves. The reaction rate can be varied based on the probability of favorable collisions of the reagents A and B. The model permits visualization of the conversion of reagents to products, and allows one to plot concentration vs. time for A, B and C. We test hypothetical reaction conditions such as: limiting reagents, the effects of reaction probabilities, and reagent concentrations on the reaction kinetics. The deterministic solutions of the reactions emerge as statistical averages in the limit of the large number of cells in the array. Modeling results for dynamic processes in the atmosphere will be presented.

Hunter, N. E.; Barton, C. C.; Seybold, P. G.; Rizki, M. M.

2012-12-01

116

Reduction of chemical reaction networks through delay distributions  

NASA Astrophysics Data System (ADS)

Accurate modelling and simulation of dynamic cellular events require two main ingredients: an adequate description of key chemical reactions and simulation of such chemical events in reasonable time spans. Quite logically, posing the right model is a crucial step for any endeavour in Computational Biology. However, more often than not, it is the associated computational costs which actually limit our capabilities of representing complex cellular behaviour. In this paper, we propose a methodology aimed at representing chains of chemical reactions by much simpler, reduced models. The abridgement is achieved by generation of model-specific delay distribution functions, consecutively fed to a delay stochastic simulation algorithm. We show how such delay distributions can be analytically described whenever the system is solely composed of consecutive first-order reactions, with or without additional ``backward'' bypass reactions, yielding an exact reduction. For models including other types of monomolecular reactions (constitutive synthesis, degradation, or ``forward'' bypass reactions), we discuss why one must adopt a numerical approach for its accurate stochastic representation, and propose two alternatives for this. In these cases, the accuracy depends on the respective numerical sample size. Our model reduction methodology yields significantly lower computational costs while retaining accuracy. Quite naturally, computational costs increase alongside network size and separation of time scales. Thus, we expect our model reduction methodologies to significantly decrease computational costs in these instances. We anticipate the use of delays in model reduction will greatly alleviate some of the current restrictions in simulating large sets of chemical reactions, largely applicable in pharmaceutical and biological research.

Barrio, Manuel; Leier, André; Marquez-Lago, Tatiana T.

2013-03-01

117

Favorite Demonstration: Demonstrating Indigo Carmine Oxidation-Reduction Reactions--A Choreography for Chemical Reactions  

NSDL National Science Digital Library

The indigo carmine demonstration (Ferguson et al. 1973), also referred to as a traffic-light demonstration (Flinn Scientific 2007a), is an example of a set of oxidation-reduction reactions that occurs within one solution. This type of demonstration can be used to introduce the concept of chemical reaction to undergraduate nonscience majors. Through their observations guided by the instructor, students begin to develop and construct the following concepts: color changes, reaction rates, reversible reactions, energy requirements (endothermic/exothermic), and equilibrium.

Majerich, David M.; Schmuckler, Joseph S.

2008-03-01

118

Gas-Phase Reactions of Halogen Species of Atmospheric Importance.  

NASA Astrophysics Data System (ADS)

Available from UMI in association with The British Library. Requires signed TDF. A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen -containing molecules and between NO_3 radicals and the iodine species I_2 and I. These experiments have shown that: (i) the reaction of methyl iodide with OH accounts for approximately 2% of the removal of CH_3I from the troposphere as compared with photolysis; (ii) abstraction of I-atoms from a C-I bond by OH is probable in the gas -phase; (iii) the halogen-containing anaesthetic substances halothane CF_3CCl BrH, enflurane CF_2HOCF _2CFClH, isoflurane CF_2HOCClHCF _3 and sevoflurane (CF_3) _2CHOCFH_2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross -sections of the compounds in the spectral region 800-1200 cm^{-1} were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl_3 for each compound. The study of the reactions between OH and CF_3CFBrH and CF _2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of reaction, the rate constant of which was found to be (1.5 +/- 0.5) times 10 ^{-12}cm^{ -3}molecule^{-1}s ^{-1}. The reaction between I and NO_3 was found to occur at a rate of about 60% of the hard-sphere collision frequency for the two species. The rate constant for reaction between I and NO_3 was found to be (4.5 +/- 1.9) times 10^{-10}cm^3 molecule^{-1}s ^{-1}. An upper limit for the heat of formation of IONO_2 of (21 +/- 3) kJmol^ {-1} was also derived. (Abstract shortened by UMI.).

Heard, Anne C.

119

Molecular Codes in Biological and Chemical Reaction Networks  

PubMed Central

Shannon’s theory of communication has been very successfully applied for the analysis of biological information. However, the theory neglects semantic and pragmatic aspects and thus cannot directly be applied to distinguish between (bio-) chemical systems able to process “meaningful” information from those that do not. Here, we present a formal method to assess a system’s semantic capacity by analyzing a reaction network’s capability to implement molecular codes. We analyzed models of chemical systems (martian atmosphere chemistry and various combustion chemistries), biochemical systems (gene expression, gene translation, and phosphorylation signaling cascades), an artificial chemistry, and random reaction networks. Our study suggests that different chemical systems posses different semantic capacities. No semantic capacity was found in the model of the martian atmosphere chemistry, the studied combustion chemistries, and highly connected random networks, i.e. with these chemistries molecular codes cannot be implemented. High semantic capacity was found in the studied biochemical systems and in random reaction networks where the number of second order reactions is twice the number of species. We conclude that our approach can be applied to evaluate the information processing capabilities of a chemical system and may thus be a useful tool to understand the origin and evolution of meaningful information, e.g. in the context of the origin of life. PMID:23372756

Gorlich, Dennis; Dittrich, Peter

2013-01-01

120

2011 Chemical Reactions at Surfaces Gordon Research Conference  

SciTech Connect

The Gordon Research Conference on Chemical Reactions at Surfaces is dedicated to promoting and advancing the fundamental science of interfacial chemistry and physics by providing surface scientists with the foremost venue for presentation and discussion of research occurring at the frontiers of their fields.

Peter Stair

2011-02-11

121

WATER AS A REACTION MEDIUM FOR CLEAN CHEMICAL PROCESSES.  

EPA Science Inventory

Green chemistry is a rapid developing new field that provides us a pro-active avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction media. The technologies generated f...

122

Relaxations, Fluctuations, Phase Transitions and Chemical Reactions in Liquid Water  

Microsoft Academic Search

Fluctuations and collective motions in liquid water and their effects on chemical reactions dynamics are analyzed. Liquid water is a `frustrated' system with multiple random hydrogen bond network structures, and has anomalous microscopic and macroscopic properties. Rearrangement dynamics of the hydrogen bond network induces collective motions of water molecules and energy fluctuations. Vibrational motions of photoexcited molecules strongly resonate to

Iwao Ohmine; Masaki Sasai

1991-01-01

123

Pressure effects in solid state chemical reactions studied by ESR  

Microsoft Academic Search

The first steps of selected solid state chemical reactions were investigated by ESR in spectral and spatial resolution. Use was made of pressure induced changes of the fine structure of Fe and Mn as Well as the dynamic Jahn-Teller effect of Cu . Paramagnetic oxygen centres like Ox were used to monitore the generation and emptying of traps in oxides,

Reinhard Stoesser

1992-01-01

124

40 CFR 799.19 - Chemical imports and exports.  

...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical...Persons who export or who intend to export chemical substances or mixtures listed in subpart B, subpart C, or subpart D of this...

2014-07-01

125

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2012 CFR

...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical...Persons who export or who intend to export chemical substances or mixtures listed in subpart B, subpart C, or subpart D of this...

2012-07-01

126

40 CFR 799.19 - Chemical imports and exports.  

Code of Federal Regulations, 2013 CFR

...CONTINUED) IDENTIFICATION OF SPECIFIC CHEMICAL SUBSTANCE AND MIXTURE TESTING REQUIREMENTS General Provisions § 799.19 Chemical...Persons who export or who intend to export chemical substances or mixtures listed in subpart B, subpart C, or subpart D of this...

2013-07-01

127

Chemical generation of atomic iodine for chemical oxygen–iodine laser. I. Modelling of reaction systems  

Microsoft Academic Search

The mathematical modelling of reaction systems for chemical generation of atomic iodine is presented. This process is aimed to be applied in the chemical oxygen–iodine laser (COIL), where it can save a substantial part of energy of singlet oxygen and so increase the laser output power. In the suggested method, gaseous reactants for I atoms generation are admixed into the

V??t Jirásek; Otomar Špalek; Jarmila Kodymová; Miroslav ?enský

2001-01-01

128

Development of a chemical oxygen - iodine laser with production of atomic iodine in a chemical reaction  

SciTech Connect

The alternative method of atomic iodine generation for a chemical oxygen - iodine laser (COIL) in chemical reactions with gaseous reactants is investigated experimentally. The influence of the configuration of iodine atom injection into the laser cavity on the efficiency of the atomic iodine generation and small-signal gain is studied. (lasers)

Censky, M; Spalek, O; Jirasek, V; Kodymova, J [Institute of Physics, Czech Academy of Sciences, Prague (Czech Republic); Jakubec, I [Institute of Inorganic Chemistry, Czech Academy of Sciences, Rez (Czech Republic)

2009-11-30

129

Energetic fuel-coolant interactions considering chemical reactions  

SciTech Connect

A propagation/expansion model developed for large scale vapor explosions was enhanced to consider the possibility of a chemical reaction between metallic fuel and the water coolant during an energetic fuel-coolant interaction (FCI). This lumped volume model, based on a fragmentation concept involving film collapse, coolant jet impingement and entrapment, predicts the correct qualitative trends for recent Sandia NPR experiments involving molten aluminum dropped into water, as a function of fuel composition, coolant temperature, ambient pressure, coolant/fuel mass ratio, and initial constraints. Chemical reactions between the molten metal and the water vapor in the surrounding film are considered and predicts aluminum ignition at 1,225 K compared to the empirically observed chemical assisted vapor explosion at 1,150 K.

Uludogan, A.; Corradini, M.L. [Univ. of Wisconsin, Madison, WI (United States)

1995-12-31

130

A Review of the Thermodynamic, Transport, and Chemical Reaction Rate Properties of High-temperature Air  

NASA Technical Reports Server (NTRS)

Thermodynamic and transport properties of high temperature air, and the reaction rates for the important chemical processes which occur in air, are reviewed. Semiempirical, analytic expressions are presented for thermodynamic and transport properties of air. Examples are given illustrating the use of these properties to evaluate (1) equilibrium conditions following shock waves, (2) stagnation region heat flux to a blunt high-speed body, and (3) some chemical relaxation lengths in stagnation region flow.

Hansen, C Frederick; Heims, Steve P

1958-01-01

131

Laboratory Kinetics of Chemical Reactions occurring in Astrophysical Environments  

NASA Astrophysics Data System (ADS)

To model the dynamics and molecular evolution of interstellar clouds, a great deal of information on chemical kinetics is required, preferably under the appropriate conditions of kinetic temperature and internal excitation. This kinetics includes (i) gas phase ionic (ion-molecule and electron-ion) and (ii) neutral-neutral reactions and (iii) heterogeneous surface catalysis, all from simple species to those as complex as polyaromatic hydrocarbons and pre-life molecules. The current situation in these three areas will be briefly reviewed with more emphasis on ionic reactions for which the most data are available. The classes of reactions will include charge and proton transfer, atom insertion and abstraction, radiative association, electron-ion and ion-ion recombination, reactions with atoms, reactions involving isotopes, reaction and production of structural isomers, ring formation and destruction, and condensation. Information on rates of reaction, product identity and state of excitation will be presented wherever possible. Some mention will also be made of the reactions of negative ions. Most recent data will be presented, specifically involving the understudied process of electron-ion recombination. Some possible future directions will also be suggested. Funding of my research program by ACF-PRF, NASA and NSF is gratefully acknowledged.

Adams, N. G.; Babcock, L. M.

2005-05-01

132

Detailed chemical kinetic reaction mechanism for biodiesel components methyl stearate and methyl oleate  

E-print Network

Detailed chemical kinetic reaction mechanism for biodiesel components methyl stearate and methyl are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate renewable sources, can reduce net emissions of greenhouse gases. An important class of biodiesel fuels

Paris-Sud XI, Université de

133

Chemical activity induces dynamical force with global structure in a reaction-diffusion-convection system  

NASA Astrophysics Data System (ADS)

We found a rotating global structure induced by the dynamical force of local chemical activity in a thin solution layer of excitable Belousov-Zhabotinsky reaction coupled with diffusion. The surface flow and deformation associated with chemical spiral waves (wavelength about 1 mm) represents a global unidirectional structure and a global tilt in the entire Petri dish (100 mm in diameter), respectively. For these observations, we scanned the condition of hierarchal pattern selection. From this result, the bromomalonic acid has an important role to induce the rotating global structure. An interaction between a reaction-diffusion process and a surface-tension-driven effect leads to such hierarchal pattern with different scales.

Mahara, Hitoshi; Okada, Koichi; Nomura, Atsushi; Miike, Hidetoshi; Sakurai, Tatsunari

2009-07-01

134

Photo-induced chemical reaction of trans-resveratrol.  

PubMed

Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25mM, 100% ethanol) under 100?Wcm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution. PMID:25308653

Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

2015-03-15

135

Information-Theoretical Complexity Analysis of Selected Elementary Chemical Reactions  

NASA Astrophysics Data System (ADS)

We investigate the complexity of selected elementary chemical reactions (namely, the hydrogenic-abstraction reaction and the identity SN2 exchange reaction) by means of the following single and composite information-theoretic measures: disequilibrium (D), exponential entropy(L), Fisher information (I), power entropy (J), I-D, D-L and I-J planes and Fisher-Shannon (FS) and Lopez-Mancini-Calbet (LMC) shape complexities. These quantities, which are functionals of the one-particle density, are computed in both position (r) and momentum (p) spaces. The analysis revealed that the chemically significant regions of these reactions can be identified through most of the single information-theoretic measures and the two-component planes, not only the ones which are commonly revealed by the energy, such as the reactant/product (R/P) and the transition state (TS), but also those that are not present in the energy profile such as the bond cleavage energy region (BCER), the bond breaking/forming regions (B-B/F) and the charge transfer process (CT). The analysis of the complexities shows that the energy profile of the abstraction reaction bears the same information-theoretical features of the LMC and FS measures, however for the identity SN2 exchange reaction does not hold a simple behavior with respect to the LMC and FS measures. Most of the chemical features of interest (BCER, B-B/F and CT) are only revealed when particular information-theoretic aspects of localizability (L or J), uniformity (D) and disorder (I) are considered.

Molina-Espíritu, M.; Esquivel, R. O.; Dehesa, J. S.

136

Tailoring oxidation degrees of graphene oxide by simple chemical reactions  

SciTech Connect

High quality graphene oxide (GO) with controllable degrees of oxidation was synthesized by simple chemical reactions inspired by approaches to unzip single wall carbon nanotubes using strong oxidizing agents. As compared to the conventional Hummers method, these reactions are less exo-therm involved without emission of toxic gases. The structural characteristics of the synthesized GO with various oxidation degrees were evaluated by x-ray diffraction, x-ray photoelectron spectroscopy, Raman spectroscopy, thermal gravimetric analysis, and UV-vis-IR spectroscopy. GO with tailored degrees of oxidation displays tunable optoelectronic properties and may have a significant impact on developing graphene- or GO-based platforms for various technological applications.

Wang Gongkai [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Sun Xiang; Lian Jie [Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Liu Changsheng [Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, Northeastern University, Shenyang, Liaoning 110004 (China)

2011-08-01

137

Quantum-chemical approach to serine formation in the interstellar medium: A possible reaction pathway  

NASA Astrophysics Data System (ADS)

Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low-temperature chemistry. The formation of amino acids, such as serine, in the interstellar medium is quite difficult. We explored the possibility of serine formation in the interstellar medium through detected interstellar molecules such as CH, CO, and OH by radical-radical and radical-neutral interactions in the gaseous phase using rigorous quantum-chemical calculations. The reaction energies, the low potential barrier and the structures of all the geometries involved in the reaction path show that serine formation is possible in interstellar space via the reaction paths.

Shivani; Singh, Amresh; Gupta, Vineet; Misra, Alka; Tandon, Poonam

2014-03-01

138

Laser studies of chemical reaction and collision processes  

SciTech Connect

This work has concentrated on several interrelated projects in the area of laser photochemistry and photophysics which impinge on a variety of questions in combustion chemistry and general chemical kinetics. Infrared diode laser probes of the quenching of molecules with {open_quotes}chemically significant{close_quotes} amounts of energy in which the energy transferred to the quencher has, for the first time, been separated into its vibrational, rotational, and translational components. Probes of quantum state distributions and velocity profiles for atomic fragments produced in photodissociation reactions have been explored for iodine chloride.

Flynn, G. [Columbia Univ., New York, NY (United States)

1993-12-01

139

Extinction and Spread of Isothemal Flame Balls in An Autocatalytic Chemical Reaction  

E-print Network

Extinction and Spread of Isothemal Flame Balls in An Autocatalytic Chemical Reaction Junping Shi(?). Remember that there are more than 4000 universities in USA! #12;An isothermal autocatalytic chemical: reaction rate Reaction-diffusion system of chemical reaction: a t = DAa - kabp, b t = DBb + kabp, t > 0, x

Shi, Jun-Ping

140

Controlling ultracold chemical reactions via Rydberg-dressed interactions  

E-print Network

We show that ultracold chemical reactions can be manipulated and controlled by using Rydberg-dressed interactions. Scattering in the ultracold regime is sensitive to long-range interactions, especially when weakly bound (or quasi-bound) states exist near the collision threshold. We investigate how, by Rydberg-dressing a reactant, one enhances its polarizability and modifies the long-range van der Waals collision complex, which can alter chemical reaction rates by shifting the position of near threshold bound states. We carry out a full quantum mechanical scattering calculation for the benchmark system H$_2$+D, and show that resonances can be moved substantially and that rate coefficients at cold and ultracold temperatures can be increased by several orders of magnitude.

Wang, Jia; Simbotin, Ion; Côté, R

2014-01-01

141

Potential for exothermic chemical reactions in waste tanks  

SciTech Connect

The potential for exothermic chemical reactions in waste tanks at Hanford is discussed. Organic chemicals have been added to Hanford waste tanks, particularly as ferrocyanides and when processing sludges at B Plant. Recent planned or ongoing activities involving stored wastes have possibly increased the potential for reaction of these wastes with nitrate salts in the waste tanks. Risk evaluations appear to be deficient in assessing the consequences of a deflagration, and in determining the probability of either a deflagration or detonation. The present question is whether current plans and recent safety-related documentation have given proper consideration to the available information about organic compounds in waste tanks. The principal organic additions to Hanford waste tanks are 1200 tonnes of organic carbon'' and 500 tonnes of Ni{sub 2}Fe(CN){sub 6}. 13 refs.

Van Tuyl, H.H.

1983-02-03

142

Tabletop imaging of structural evolutions in chemical reactions  

E-print Network

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using VUV light from a Free Electron Laser [Phys. Rev. Lett. 105, 263002 (2010)]. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond-breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and definitively quantitative ab initio trajectory simulations.

Ibrahim, Heide; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

2014-01-01

143

Boundary Effects on Chaotic Advection-Diffusion Chemical Reactions M. Chertkov1  

E-print Network

not sense changes in the chemical concentrations nor heat released in the result of the chemical reactionBoundary Effects on Chaotic Advection-Diffusion Chemical Reactions M. Chertkov1 and V. Lebedev1,2 1 chemical reaction, A B ! C, in a statistically stationary bounded chaotic flow at large Peclet number Pe

Lebedev, Vladimir

144

Quantum Low-Temperature Limit of a Chemical Reaction Rate  

Microsoft Academic Search

The radiation-induced polymerization of formaldehyde has been studied in the solid state. The time of addition of one new link to a polymer chain increases exponentially in accordance with the Arrhenius law at 140 to 80 K, but approaches a constant value (approximately 10-2 second) at temperatures below 10 K. Thus, a low-temperature limit to a chemical reaction rate has

V. I. Goldanskii; M. D. Frank-Kamenetskii; I. M. Barkalov

1973-01-01

145

Chemical Reaction-Induced Multi-molecular Polarization (CRIMP).  

PubMed

Here we present a novel hyperpolarization method, Chemical Reaction-Induced Multi-molecular Polarization (CRIMP), which could be applied to the study of several in vivo processes simultaneously including glycolysis, TCA cycle, fatty acid synthesis and pH mapping. Through the use of non-enzymatic decarboxylation, we generate four hyperpolarized imaging agents from hyperpolarized 1,2-(13)C pyruvic acid. PMID:25224323

Lee, Y; Zacharias, N M; Piwnica-Worms, D; Bhattacharya, P K

2014-10-01

146

Different chemical reaction times between normal and solid cancer cells.  

PubMed

Entropy generation approach has been developed in order to use it for the analysis of complex systems with particular regards to biological systems in order to evaluate their stationary states. The entropy generation is related to the transport processes related to energy flows. Moreover, cancer can be described as an open complex dynamic and self-organizing system. Using the entropy generation approach it is possible to point out different chemical reaction time between normal and solid cancer cells. PMID:23643705

Lucia, Umberto

2013-07-01

147

Great Chemistry! How is Energy Released in Chemical Reactions?  

NSDL National Science Digital Library

The Materials Science and Technology Teacher's Workshop (MAST) provides this activity to look at the ways in which energy is released in chemical reactions. The class will examine plaster of paris, bromthymol blue and the hydration of baking soda. Students will observe the temperature changes of each.The lesson includes step by step directions for the experiment. Discussion questions and teacher notes are also included.

2012-07-23

148

Chemical reactions in the Titan’s troposphere during lightning  

NASA Astrophysics Data System (ADS)

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH 4/N 2 atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan's lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan's surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan's atmosphere are H 2, HCN, C 2N 2, C 2H 2, C 2H 4, C 2H 6, NH 3 and H 2CN. The annual production of these compounds was estimated in the Titan's atmosphere.

Kovács, Tamás; Turányi, Tamás

2010-06-01

149

Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions  

SciTech Connect

A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

Gray, S.K. [Argonne National Laboratory, IL (United States)

1993-12-01

150

Importance of toxicokinetics for interspecies variation in sensitivity to chemicals.  

PubMed

Interspecies variation in sensitivity to synthetic chemicals can be orders of magnitude large. Species traits causing the variation can be related to toxicokinetics (uptake, distribution, biotransformation, elimination) or toxicodynamics (interaction with biological target sites). We present an approach to systematically measure and model the contribution of uptake, biotransformation, internal distribution, and elimination kinetics toward species sensitivity differences. The aim is to express sensitivity as target tissue specific, internal lethal concentrations. A case study with the pesticides diazinon, imidacloprid, and propiconazole and the aquatic invertebrates Gammarus pulex, Gammarus fossarum, and Lymnaea stagnalis illustrates the approach. L. stagnalis accumulates more pesticides than Gammaridae when measured in whole organisms but less in target tissues such as the nervous system. Toxicokinetics, i.e. biotransformation and distribution, explain the higher tolerance of L. stagnalis to the insecticide diazinon when compared to Gammaridae. L. stagnalis was again more tolerant to the other neurotoxicant imidacloprid; however, the difference in sensitivity could not be explained by toxicokinetics alone, indicating the importance of toxicodynamic differences. Sensitivity to propiconazole was comparable among all species and, when expressed as internal lethal concentrations, falls in the range of baseline toxicity. PMID:24758734

Nyman, Anna-Maija; Schirmer, Kristin; Ashauer, Roman

2014-05-20

151

APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems  

SciTech Connect

Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

Nguyen, H.D.

1991-11-01

152

APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems  

SciTech Connect

Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

Nguyen, H.D.

1991-11-01

153

Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.  

PubMed

Computational approaches to understanding chemical reaction mechanisms generally begin by establishing the relative energies of the starting materials, transition state, and products, that is, the stationary points on the potential energy surface of the reaction complex. Examining the intervening species via the intrinsic reaction coordinate (IRC) offers further insight into the fate of the reactants by delineating, step-by-step, the energetics involved along the reaction path between the stationary states. For a detailed analysis of the mechanism and dynamics of a chemical reaction, the reaction path Hamiltonian (RPH) and the united reaction valley approach (URVA) are an efficient combination. The chemical conversion of the reaction complex is reflected by the changes in the reaction path direction t(s) and reaction path curvature k(s), both expressed as a function of the path length s. This information can be used to partition the reaction path, and by this the reaction mechanism, of a chemical reaction into reaction phases describing chemically relevant changes of the reaction complex: (i) a contact phase characterized by van der Waals interactions, (ii) a preparation phase, in which the reactants prepare for the chemical processes, (iii) one or more transition state phases, in which the chemical processes of bond cleavage and bond formation take place, (iv) a product adjustment phase, and (v) a separation phase. In this Account, we examine mechanistic analysis with URVA in detail, focusing on recent theoretical insights (with a variety of reaction types) from our laboratories. Through the utilization of the concept of localized adiabatic vibrational modes that are associated with the internal coordinates, q(n)(s), of the reaction complex, the chemical character of each reaction phase can be identified via the adiabatic curvature coupling coefficients, A(n,s)(s). These quantities reveal whether a local adiabatic vibrational mode supports (A(n,s) > 0) or resists (A(n,s) < 0) the curving of the path, and thus the structural changes of the reaction complex. URVA can show the mechanism of a reaction expressed in terms of reaction phases, revealing the sequence of chemical processes in the reaction complex and making it possible to determine those electronic factors that control the mechanism and energetics of the reaction. The magnitude of adiabatic curvature coupling coefficients is related to strength and polarizability of the bonds being broken. Transient points along the reaction path are associated with hidden intermediates and hidden transition states, which can be converted into real intermediates and transition states when the reaction conditions or the substitution pattern of the reaction complex are appropriately changed. Accordingly, URVA represents a theoretical tool with tremendous experimental potential, offering the chemist the ability to assert greater control over reactions. PMID:20232791

Kraka, Elfi; Cremer, Dieter

2010-05-18

154

Examining the importance of dynamics, barrier compression and hydrogen tunnelling in enzyme catalysed reactions  

Microsoft Academic Search

Nuclear quantum mechanical tunnelling is important in enzyme-catalysed H-transfer reactions. This viewpoint has arisen after a number of experimental studies have described enzymatic reactions with kinetic isotope effects that are significantly larger than the semiclassical limit. Other experimental evidence for tunnelling, and the potential role of promoting vibrations that transiently compress the reaction barrier, is more indirect, being derived from

Sam Hay; Nigel S. Scrutton

2011-01-01

155

Compare and contrast the reaction coordinate diagrams for chemical reactions and cytoskeletal force generators  

PubMed Central

Reaction coordinate diagrams are used to relate the free energy changes that occur during the progress of chemical processes to the rate and equilibrium constants of the process. Here I briefly review the application of these diagrams to the thermodynamics and kinetics of the generation of force and motion by cytoskeletal motors and polymer ratchets as they mediate intracellular transport, organelle dynamics, cell locomotion, and cell division. To provide a familiar biochemical context for discussing these subcellular force generators, I first review the application of reaction coordinate diagrams to the mechanisms of simple chemical and enzyme-catalyzed reactions. My description of reaction coordinate diagrams of motors and polymer ratchets is simplified relative to the rigorous biophysical treatment found in many of the references that I use and cite, but I hope that the essay provides a valuable qualitative representation of the physical chemical parameters that underlie the generation of force and motility at molecular scales. In any case, I have found that this approach represents a useful interdisciplinary framework for understanding, researching, and teaching the basic molecular mechanisms by which motors contribute to fundamental cell biological processes. PMID:23408787

Scholey, Jonathan M.

2013-01-01

156

Reaction Networks for Interstellar Chemical Modelling: Improvements and Challenges  

NASA Astrophysics Data System (ADS)

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes—ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination—is reviewed. Emphasis is placed on those key reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalyzed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.

Wakelam, V.; Smith, I. W. M.; Herbst, E.; Troe, J.; Geppert, W.; Linnartz, H.; Öberg, K.; Roueff, E.; Agúndez, M.; Pernot, P.; Cuppen, H. M.; Loison, J. C.; Talbi, D.

2010-10-01

157

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories  

NASA Technical Reports Server (NTRS)

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Gokoglu, Suleyman A.

1988-01-01

158

Crossed beam reaction of cyano radicals with hydrocarbon molecules. IV. Chemical dynamics of cyanoacetylene ,,HCCCN; X 1  

E-print Network

reaction to be included in reaction networks modeling the chemistry in dark, molecular clouds, outflow is an important means to test chemical models on the evolution of cold dark molecular clouds. The HC3N isomers- culations, this model suggested a recombination of interstel- lar HCCCNH ions with an electron from

Kaiser, Ralf I.

159

Automated microreactor system for reaction development and online optimization of chemical processes  

E-print Network

Developing the optimal conditions for chemical reactions that are common in fine chemical and pharmaceutics is a difficult and expensive task. Because syntheses in these fields have multiple reaction pathways, a significant ...

McMullen, Jonathan Patrick

2010-01-01

160

Miscible viscous fingering with chemical reaction involving precipitation.  

NASA Astrophysics Data System (ADS)

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. The present study has experimentally examined how precipitation produced by chemical reaction affects miscible viscous fingering pattern. A 97 wt % glycerin solution containing iron(III) nitrate (yellow) and a solution containing potassium hexacyano ferrate(II) (colorless) were used as the more- and less-viscous liquids, respectively. In this case, the chemical reaction instantaneously takes place and produces the precipitation being dark blue in color. The experiments were done by varying reactant concentrations, the cell's gap width, and the displacement speed. We compared the patterns involving the precipitation reaction with those in the non-reactive cases. We have found fylfot-like pattern is observed, depending on the experimental condition, which has never been formed in the non-reactive experiments. As the reactant concentrations are increased or the displacement speed is decreased, the effects of the precipitation on the patterns are more pronounced.

Bae, Si-Kyun; Nagatsu, Yuichiro; Kato, Yoshihito; Tada, Yutaka

2007-11-01

161

Thermal energy storage. [by means of chemical reactions  

NASA Technical Reports Server (NTRS)

The principles involved in thermal energy storage by sensible heat, chemical potential energy, and latent heat of fusion are examined for the purpose of evolving selection criteria for material candidates in the low ( 0 C) and high ( 100 C) temperature ranges. The examination identifies some unresolved theoretical considerations and permits a preliminary formulation of an energy storage theory. A number of candidates in the low and high temperature ranges are presented along with a rating of candidates or potential candidates. A few interesting candidates in the 0 to 100 C region are also included. It is concluded that storage by means of reactions whose reversibility can be controlled either by product removal or by catalytic means appear to offer appreciable advantages over storage with reactions whose reversability cannot be controlled. Among such advantages are listed higher heat storage capacities and more favorable options regarding temperatures of collection, storage, and delivery. Among the disadvantages are lower storage efficiencies.

Grodzka, P. G.

1975-01-01

162

A quantum informational approach for dissecting chemical reactions  

E-print Network

We present a conceptionally different approach to dissect bond-formation processes in metal-driven catalysis using concepts from quantum information theory. Our method uses the entanglement and correlation among molecular orbitals to analyze changes in electronic structure that accompany chemical processes. As a proof-of-principle example, the evolution of nickel-ethene bond-formation is dissected which allows us to monitor the interplay of back-bonding and $\\pi$-donation along the reaction coordinate. Furthermore, the reaction pathway of nickel-ethene complexation is analyzed using quantum chemistry methods revealing the presence of a transition state. Our study supports the crucial role of metal-to-ligand back-donation in the bond-forming process of nickel-ethene.

Duperrouzel, Corinne; Boguslawski, Katharina; Barcza, Gergerly; Legeza, Örs; Ayers, Paul W

2014-01-01

163

Nature of the chemical reaction for furfural modified asphalt  

SciTech Connect

Three of the most serious problems of asphalt pavements today are rutting, cracking, and susceptibility to moisture damage (stripping). Asphalt manufacturers have been mixing asphalts with polymers to produce polymer-modified asphalts with improved rheological properties. However, the costs for these improved polymer-modified asphalts are almost double that of regular asphalts. FHWA researchers have found that asphalt modified by the chemical, furfural (which is prepared by simple elimination reaction of aldopentoses obtained from oat hulls), exhibited better stripping properties and was less temperature susceptible than the virgin asphalt while costing less than polymer-modified asphalts. This paper discusses the possible structure of the furfural-modified asphalt, data for the virgin and furfural-modified asphalts and their Corbett fractions, data from a model reaction between phenol and furfural, and a possible explanation of this structure based on these data.

Memon, G.M.; Chollar, B.H. [FHWA Engineering, Inc., McLean, VA (United States)

1994-12-31

164

Chemical reaction network theory for in-silico biologists Jeremy Gunawardena  

E-print Network

Chemical reaction network theory for in-silico biologists Jeremy Gunawardena Bauer Center@cgr.harvard.edu June 20, 2003 Contents 1 Introduction 1 2 Chemical reaction networks 2 3 Linearity in chemical reaction biological systems evidently exhibit more complex behaviours, such as oscillations, [18], the significance

Gunawardena, Jeremy

165

Method for detecting pollutants. [through chemical reactions and heat treatment  

NASA Technical Reports Server (NTRS)

A method is described for detecting and measuring trace amounts of pollutants of the group consisting of ozone, nitrogen dioxide, and carbon monoxide in a gaseous environment. A sample organic solid material that will undergo a chemical reaction with the test pollutant is exposed to the test environment and thereafter, when heated in the temperature range of 100-200 C., undergoes chemiluminescence that is measured and recorded as a function of concentration of the test pollutant. The chemiluminescence of the solid organic material is specific to the pollutant being tested.

Rogowski, R. S.; Richards, R. R.; Conway, E. J. (inventors)

1976-01-01

166

Exploring chemical diversity via a modular reaction pairing strategy  

E-print Network

1293 Exploring chemical diversity via a modular reaction pairing strategy Joanna K. Loh1, Sun Young Yoon1, Thiwanka B. Samarakoon1, Alan Rolfe1, Patrick Porubsky2, Benjamin Neuenswander2, Gerald H. Lushington1,2 and Paul R. Hanson*1,2 Full Research... representative compounds. [http://www.beilstein-journals.org/bjoc/content/ supplementary/1860-5397-8-147-S1.pdf] Acknowledgements Financial support of this work was provided by the National Institute of General Medical Sciences and is gratefully acknowl- edged (P...

Loh, Joanna K.; Yoon, Sun Young; Samarakoon, Thiwanka Bandara; Rolfe, Alan; Porubsky, Patrick R.; Neuenswander, Benjamin; Lushington, Gerald H.; Hanson, Paul R.

2012-08-15

167

Building robust chemical reaction mechanisms : next generation of automatic model construction software  

E-print Network

Building proper reaction mechanisms is crucial to model the system dynamic properties for many industrial processes with complex chemical reaction phenomena. Because of the complexity of a reaction mechanism, computer-aided ...

Song, Jing, 1972-

2004-01-01

168

Temporal disorder and fluctuation theorem in chemical reactions.  

PubMed

We report the analytical study of a class of chemical reactions described as birth-and-death stochastic processes ruled by a master equation compatible with the mass action law of chemical kinetics. We solve analytically this master equation to find the generating functions of the fluctuating fluxes and of the Lebowitz-Spohn action functional. These generating functions are explicitly shown to obey fluctuation theorems. In the case of fluxes, we derive relations for the nonlinear response coefficients, extending Onsager's reciprocity relations. Moreover, symmetry relations reminiscent of the fluctuation theorem are obtained for the finite-time probability distributions of the fluxes. The temporal disorder of the stochastic process is also characterized and related to the thermodynamic entropy production. PMID:18517359

Andrieux, David; Gaspard, Pierre

2008-03-01

169

Chemical modification of graphene via hyperthermal molecular reaction.  

PubMed

Chemical functionalization of graphene is achieved by hyperthermal reaction with azopyridine molecular ions. The one-step, room temperature process takes place in high vacuum (10(-7) mbar) using an electrospray ion beam deposition (ES-IBD) setup. For ion surface collisions exceeding a threshold kinetic energy of 165 eV, molecular cation beams of 4,4'-azobis(pyridine) covalently attach to chemical vapor deposited (CVD) graphene. A covalent functionalization degree of 3% of the carbon atoms of graphene is reached after 3-5 h of ion exposure of 2 × 10(14) azopyridinium/cm(2) of which 50% bind covalently. This facile approach for the controlled modification of graphene extends the scope of candidate species that would not otherwise react via existing conventional methods. PMID:25185758

Dubey, Girjesh; Urcuyo, Roberto; Abb, Sabine; Rinke, Gordon; Burghard, Marko; Rauschenbach, Stephan; Kern, Klaus

2014-10-01

170

SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF  

E-print Network

SHEAR LOCALIZATION AND CHEMICAL REACTION IN HIGH-STRAIN, HIGH-STRAIN-RATE DEFORMATION OF Ti.6±1 mm. Thermodynamic and kinetic calculations yield the reaction rate outside the shear bands a decisive role in accelerating chemical reactions, particularly, converting an exothermic reaction

Meyers, Marc A.

171

Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions  

NASA Technical Reports Server (NTRS)

Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

Johnson, R. E.

1986-01-01

172

Single-molecule chemical reactions: Reexamination of the Kramers approach G. Margolin1  

E-print Network

on chemical conformational changes, and simple chemical processes in condensed phase environments, for exampleSingle-molecule chemical reactions: Reexamination of the Kramers approach G. Margolin1 and E; published 2 August 2005 Single-molecule chemical reactions yield insight into fluctuation phenomena

Barkai, Eli

173

Solar-chemical energy conversion via reversible liquid phase Diels-Alder reactions. Final technical report  

Microsoft Academic Search

Thermochemical energy conversion at moderate or low temperature (< about 400°C) employing liquid phase components throughout a cycle is suggested as a promising concept for high-efficiency conversion of solar energy to a convenient chemical form. In particular, we propose liquid phase Diels-Alder cycloaddition chemistry as an important class of reversible reactions for such low or moderate temperature thermochemical energy conversion

T. G. Lenz; L. S. Hegedus; J. D. Vaughan

1983-01-01

174

Laser enhanced chemical reaction studies. Technical progress report  

SciTech Connect

A powerful infrared diode laser probe was used to determine final states of small (2-5 atom) molecules produced by collisions, photofragmentation, or chemical reactions with spectral resolution 0.0003 cm{sup {minus}1} and time resolution 10{sup {minus}7}s. Besides picturing the vibrational rotational quantum states of product molecules, this also provides a picture of the translational motion of recoiling fragments through the infrared Doppler line width profile. This method was used to probe collisions between cool bath molecules and vibrationally hot molecules, in order to understand the quenching mechanism for unimolecular chemical reactions. Long-range collisions appear to dominate production of bath molecules which become vibrationally excited during this quenching process. Glimpses are being provided of the separate behavior of translational and rotational degrees of freedom of recoiling bath molecules during relaxation of highly vibrationally excited donors. A study was completed of collisions between hot H atoms and CO{sub 2}, by measuring probability for excitation of the antisymmetric vibrational overtone level CO{sub 2}(00{sup 0}2). Comparison with a 00{sup 0}1 fundamental level study suggests that translational and rotational energy distributions in this collision can be described by classical mechanics, but that vibrational excitation probabilities require full quantum treatment. Relaxation of hot pyrazine by CO{sub 2} was studied. Multiphoton ionization studies have been begun.

Flynn, G.

1993-12-31

175

TOPICAL REVIEW: Plasma-chemical reactions: low pressure acetylene plasmas  

NASA Astrophysics Data System (ADS)

Reactive plasmas are a well-known tool for material synthesis and surface modification. They offer a unique combination of non-equilibrium electron and ion driven plasma chemistry, energetic ions accelerated in the plasma sheath at the plasma-surface interface, high fluxes of reactive species towards surfaces and a friendly environment for thermolabile objects. Additionally, small negatively charged clusters can be generated, because they are confined in the positive plasma potential. Plasmas in hydrocarbon gases, and especially in acetylene, are a good example for the discussion of different plasma-chemical processes. These plasmas are involved in a plethora of possible applications ranging from fuel conversion to formation of single wall carbon nanotubes. This paper provides a concise overview of plasma-chemical reactions (PCRs) in low pressure reactive plasmas and discusses possible experimental and theoretical methods for the investigation of their plasma chemistry. An up-to-date summary of the knowledge about low pressure acetylene plasmas is given and two particular examples are discussed in detail: (a) Ar/C2H2 expanding thermal plasmas with electron temperatures below 0.3 eV and with a plasma chemistry initiated by charge transfer reactions and (b) radio frequency C2H2 plasmas, in which the energetic electrons mainly control PCRs.

Benedikt, J.

2010-02-01

176

Investigation of primary chemical reactions of electrons by emission Mössbauer and positron spectroscopies  

NASA Astrophysics Data System (ADS)

A set of early chemical reactions induced in frozen medium around decayed 57Co or 119mSn nuclei by emitted Auger electrons is suggested. The mechanism predicts a correlation between formation probabilities of final products, namely Fe2+-Fe3+ or Sn2+-Sn4+ ions, positronium atom and molecular hydrogen formed in similar medium after its irradiation by fast positrons and electrons. This correlation indicates a similarity of chemical processes occurring in nanovolumes around Mössbauer 57Fe- and 119Sn-nuclei after radioactive decay as well as in tracks produced by fast positrons and electrons. The important role of quasi-free electrons is revealed.

Byakov, Vsevolod M.; Kulikov, Leonid A.; Perfil'Ev, Yurii D.; Stepanov, Sergey V.

2005-11-01

177

Irreversible bimolecular chemical reactions on directed scale-free networks  

NASA Astrophysics Data System (ADS)

Kinetics of irreversible bimolecular chemical reactions A+A?0 and A+B?0 on directed scale-free networks with the in-degree distribution Pin(k)˜k-?in and the out-degree distribution Pout(?)˜?-?out are investigated. Since the correlation between k and ? of each node generally exists in directed networks, we control the correlation with the probability r?[0,1] by two different algorithms for the construction of the directed networks, i.e., the so-called k and ? algorithms. For r=1, the k algorithm gives =, whereas the ? algorithm gives =. For r=0, = for both algorithms. The kinetics of both reactions are analyzed using heterogeneous mean-field (HMF) theory and Monte Carlo simulations. The density of particles (?) algebraically decays in time t as ?(t)˜t-?. The kinetics of both reactions are determined by the same rate equation, d?/dt=a?2+b??-1, apart from coefficients. The exponent ? is determined by the algorithm: ?=?in for the k algorithm (r?0) and ?=?min for the ? algorithm (r>0), where ?min is the smaller exponent between ?in and ?out. For ?>3, one observes the ordinary mean-field kinetics, ?˜1/t (?=1). In contrast, for ?<3, ?(t) anomalously decays with ?=1/(?-2). The HMF predictions are confirmed by the simulations on quenched directed networks.

Kwon, Sungchul; Kim, Yup

2013-10-01

178

Assessment of reaction-rate predictions of a collision-energy approach for chemical reactions in atmospheric flows.  

SciTech Connect

A recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates is assessed for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological nonequilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, significant differences can be found. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

2010-06-01

179

Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review  

NASA Astrophysics Data System (ADS)

This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several difficulties (both semantic and experimental) that recur in the studies reviewed are discussed. The subtle effects of various sterilization techniques on extracellular biochemicals and complex chemical reducing agents in sediment have stifled attempts to separate abiotic from biological degradation reactions. The characterization of redox conditions in a natural system is still problematic since measured redox potential is not adequate. Suggestions for future research toward a process-level understanding of abiotic chemical reductions are made.

Macalady, Donald L.; Tratnyek, Paul G.; Grundl, Timothy J.

1986-02-01

180

Titan's Interior Chemical Composition: Possible Important Phase Transitions  

NASA Astrophysics Data System (ADS)

We study the interior composition of Titan using thermal chemical equilibrium calculations that are valid to high pressures and temperatures. The equations of state are based on exponential-6 fluid theory and have been validated against experimental data up to a few Mbars in pressure and approximately 20000K in temperature. In addition to CHNO molecules, we account for multi-phases of carbon, water and a variety of metals such as Al and Fe, and their oxides. With these fluid equations of state, chemical equilibrium is calculated for a set of product species. As the temperature and pressure evolves for increasing depth in the interior, the chemical equilibrium shifts. We assume that Titan is initially composed of comet material, which we assume to be solar, except for hydrogen, which we take to be depleted by a factor 1/1000. We find that a significant amount of nitrogen is in the form of N2, rather than NH3. Moreover, above 12 kbars pressure, as is the interior pressure of Titan, a significant amount of the carbon is in the form of graphite, rather than CO2 and CH4. We discuss the implications of these results for understanding the atmospheric and surface composition of Titan. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Howard, Michael; Fried, L. E.; Khare, B. N.; McKay, C. P.

2008-09-01

181

Modeling of Sheath Ion-Molecule Reactions in Plasma Enhanced Chemical Vapor Deposition of Carbon Nanotubes  

NASA Technical Reports Server (NTRS)

In many plasma simulations, ion-molecule reactions are modeled using ion energy independent reaction rate coefficients that are taken from low temperature selected-ion flow tube experiments. Only exothermic or nearly thermoneutral reactions are considered. This is appropriate for plasma applications such as high-density plasma sources in which sheaths are collisionless and ion temperatures 111 the bulk p!asma do not deviate significantly from the gas temperature. However, for applications at high pressure and large sheath voltages, this assumption does not hold as the sheaths are collisional and ions gain significant energy in the sheaths from Joule heating. Ion temperatures and thus reaction rates vary significantly across the discharge, and endothermic reactions become important in the sheaths. One such application is plasma enhanced chemical vapor deposition of carbon nanotubes in which dc discharges are struck at pressures between 1-20 Torr with applied voltages in the range of 500-700 V. The present work investigates The importance of the inclusion of ion energy dependent ion-molecule reaction rates and the role of collision induced dissociation in generating radicals from the feedstock used in carbon nanotube growth.

Hash, David B.; Govindan, T. R.; Meyyappan, M.

2004-01-01

182

Waste Heat Recovery from Blast Furnace Slag by Chemical Reactions  

NASA Astrophysics Data System (ADS)

Blast furnace (BF) slag, which is the main byproduct in the ironmaking process, contains large amounts of sensible heat. To recover the heat, a new waste heat-recovery system—granulating molten BF slag by rotary multinozzles cup atomizer and pyrolyzing printed circuited board with obtained hot BF slag particle—was proposed in this study. The feasibility of the waste heat-recovery system was verified by dry granulation and pyrolyzation experiments. The energy of hot BF slag could be converted to chemical energy through the pyrolysis reaction, and a large amount of combustible gas like CO, H2, C m H n , and CH4 can be generated during the process.

Qin, Yuelin; Lv, Xuewei; Bai, Chenguang; Qiu, Guibao; Chen, Pan

2012-08-01

183

Review of OCS gas-phase reactions in dark cloud chemical models  

E-print Network

The association reaction S + CO {\\to} OCS + hnu has been identified as being particularly important for the prediction of gas-phase OCS abundances by chemical models of dark clouds. We performed detailed ab-initio calculations for this process in addition to undertaking an extensive review of the neutral-neutral reactions involving this species which might be important in such environments. The rate constant for this association reaction was estimated to be several orders of magnitude smaller than the one present in current astrochemical databases. The new rate for this reaction and the introduction of other processes, notably OH + CS {\\to} OCS + H and C + OCS {\\to} CO + CS, dramatically changes the OCS gas-phase abundance predicted by chemical models for dark clouds. The disagreement with observations in TMC-1 (CP) and L134N (N), suggests that OCS may be formed on grain surfaces as is the case for methanol. The observation of solid OCS on interstellar ices supports this hypothesis.

Loison, Jean-Christophe; Bergeat, Astrid; Hickson, Kevin M; Wakelam, Valentine

2012-01-01

184

Importance of airway inflammation for late asthmatic reactions induced by toluene diisocyanate in sensitized subjects.  

PubMed

To determine the importance of airway inflammation for late asthmatic reactions and increased airway responsiveness induced by TDI, we investigated whether late asthmatic reactions and increased responsiveness induced by TDI are associated with airway inflammation and whether steroids prevent them by modifying the inflammatory response within the airways. We measured FEV1 before and at regular intervals after exposure to TDI and performed dose-response curves to methacholine and bronchoalveolar lavage 8 hr after TDI in two subjects with previously documented late asthmatic reaction; then we repeated the same procedure a few weeks after treatment with steroids. Airway responsiveness and polymorphonuclear cells were increased in both subjects after the late asthmatic reaction; treatment with steroids prevented late asthmatic reaction and the increase in airway responsiveness and polymorphonuclear cells in bronchoalveolar lavage. These results suggest that late asthmatic reaction induced by TDI may be caused by airway inflammation. PMID:2823559

Boschetto, P; Zocca, E; Bruchi, O; Cappellazzo, G; Milani, G F; Pivirotto, F; Mapp, C E; Fabbri, L M

1987-01-01

185

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is the final technical report for the project titled 'Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks'. The aim of the project was to develop an efficient chemistry model for combustion simulations. The reduced chemistry model was developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) was used via a new network topology known as Non-linear Principal Components Analysis (NPCA). A commonly used Multilayer Perceptron Neural Network (MLP-NN) was modified to implement NPCA-NN. The training rate of NPCA-NN was improved with the GEneralized Regression Neural Network (GRNN) based on kernel smoothing techniques. Kernel smoothing provides a simple way of finding structure in data set without the imposition of a parametric model. The trajectory data of the reaction mechanism was generated based on the optimization techniques of genetic algorithm (GA). The NPCA-NN algorithm was then used for the reduction of Dimethyl Ether (DME) mechanism. DME is a recently discovered fuel made from natural gas, (and other feedstock such as coal, biomass, and urban wastes) which can be used in compression ignition engines as a substitute for diesel. An in-house two-dimensional Computational Fluid Dynamics (CFD) code was developed based on Meshfree technique and time marching solution algorithm. The project also provided valuable research experience to two graduate students.

Ziaul Huque

2007-08-31

186

Chemical reactions of excited nitrogen atoms for short wavelength chemical lasers. Final technical report  

SciTech Connect

Accomplishments of this program include the following: (1) Scalable, chemical generation of oxygen atoms by reaction of fluorine atoms and water vapor. (2) Production of nitrogen atom densities of 1 {times} 10{sup 1}5 cm{sup {minus}3} with 5% electrical efficiency by injecting trace amounts of fluorine into microwave discharged nitrogen. (3) Production of cyanide radicals by reaction of high densities of N atoms with cyanogen. (4) Production of carbon atoms by reaction of nitrogen atoms with cyanogen or with fluorine atoms and hydrogen cyanide. (5) Confirmation that the reaction of carbon atoms and carbonyl sulfide produces CS(a{sup 3} {Pi}{sub r}), as predicted by conservation of electron spin and orbital angular momenta and as proposed by others under another SWCL program. (6) Production of cyanide radicals by injection of cyanogen halides into active nitrogen and use as spectroscopic calibration source. (7) Demonstration that sodium atoms react with cyanogen chloride, bromide and iodide and with cyanuric trifluoride to produce cyanide radicals. (8) Demonstration of the potential utility of the fluorine atom plus ammonia reaction system in the production of NF(b{sup l}{Sigma}{sup +}) via N({sup 2}D) + F{sub 2}.

Not Available

1989-12-15

187

A catalyst is an agent that modifies the kinetics of a chemical reaction, making it occur faster, but is not itself consumed as  

E-print Network

A catalyst is an agent that modifies the kinetics of a chemical reaction, making it occur faster, but is not itself consumed as part of the reaction. Catalysts are essential for commercial production of a number of economically important commodity and specialty chemicals. For transition metals, oxidation states are related

188

Direct Monte Carlo simulation of chemical reaction systems: Prediction of ultrafast detonations  

E-print Network

-dimensional flow with the reaction A MB M having variable energy release and rate characteristics. For a slow by the energy released by exothermic chemical reaction within the wave. A com- plete theoretical treatmentDirect Monte Carlo simulation of chemical reaction systems: Prediction of ultrafast detonations

Anderson, James B.

189

Progression in High School Students' (Aged 16-18) Conceptualizations about Chemical Reactions in Solution.  

ERIC Educational Resources Information Center

Explores the development over time of students' understandings of the concept of chemical reaction in the context of two familiar reactions in solution. Based on interviews (n=48), results show that students made some progress in their understanding of the concept of chemical reaction but some fundamental misconceptions remained. (Author/MM)

Boo, Hong-Kwen; Watson, J. R.

2001-01-01

190

MODEL OF CHEMICAL REACTION EQUILIBRIUM OF SULFURIC ACID SALTS OF TRIOCTYLAMINE  

Microsoft Academic Search

The chemical reaction of trioctylamine (TOA) and sulfuric acid in organic solvent\\/aqueous solution was carried out. TOA salt products of various kinds were obtained based on different conditions of operation and organic solvents. An equilibrium model, based on the chemical reaction of sulfuric acid and trioctylamine, is proposed. The equilibrium constants of various reactions of trioctylamine and sulfuric acid were

MAW-LING WANG; KWAN-HUA HU

1993-01-01

191

Effect of the reversibility of the chemical reaction on triple flames  

Microsoft Academic Search

We examine a new aspect of triple flames, namely the effect of the reversibility of the chemical reaction on flame propagation. The study is carried out in the configuration of the two-dimensional strained mixing layer formed between two opposing streams of fuel and oxidiser. The chemical reaction is modelled as a single reversible reaction following an Arrhenius law in the

Samina Ali; Joel Daou

2007-01-01

192

Experimental Re-Examination of the Law of Conservation of Mass in Chemical Reactions  

Microsoft Academic Search

At the beginning of the century the law of conservation of mass in chemical reactions was checked experimentally by Landolt and various other experimenters. Even though in 8 of the 10 chemical reactions studied by Landolt the validity of conservation of mass was confirmed within the margin of experimental errors, in 2 reactions the pre vs. post comparison of the

KLAUS VOLKAMER; CHRISTOPH STREICHER; KENNETH G. WALTON; JOHN FAGAN

193

A Comprehensive Chemical Kinetic Reaction Mechanism for Oxidation and Pyrolysis of Propane and Propene  

Microsoft Academic Search

Abstract—A detailed chemical kinetic reaction mechanism is developed to describe the oxidation and pyrolysis of propane and propene. The mechanism consists of 163 elementary reactions among 4l chemical species. New rate expressions are developed for a number of reactions of propane, propene, and intermediate hydrocarbon species with radicals including H, 0, and OH. The mechanism is tested by comparisons between

CHARLES K. WESTBROOK; WILLIAM J. PITZ

1984-01-01

194

Process for providing a feed gas for a chemical reaction and for the separation of a gaseous reaction product  

SciTech Connect

A process is claimed for providing a feed gas for a chemical reaction and for separating a gaseous reaction product from the gaseous mixture obtained by the reaction. The feed gas is obtained by the fractionation of a crude gas mixture containing this feed gas proper, as well as a carrier gas or carrier gas mixture, and is reacted only incompletely in the reaction, and the unreacted proportion is recycled into the reaction. The improvement is obtained by conducting the fractionation of the crude gas mixture and the separation of the gaseous reaction product in a single adsorption plant operating by the pressure swing method and containing cyclically reversible adsorbers.

Benkmann, C.; Lassmann, E.

1981-07-28

195

Solar-chemical energy conversion via reversible liquid phase Diels-Alder reactions. Final technical report  

SciTech Connect

Thermochemical energy conversion at moderate or low temperature (< about 400/sup 0/C) employing liquid phase components throughout a cycle is suggested as a promising concept for high-efficiency conversion of solar energy to a convenient chemical form. In particular, we propose liquid phase Diels-Alder cycloaddition chemistry as an important class of reversible reactions for such low or moderate temperature thermochemical energy conversion systems. One of the important attributes of thermally driven Diels-Alder reactions is their concerted mechanism, with consequent high yields and efficiencies relative to liquid photochemical systems. Since the systems we propose involve organic species, with thermal stability concerns about 400/sup 0/C, it is important to demonstrate equilibrium shift capability for the highly energetic reactions sought. We have therefore carried out experimental studies with model liquid Diels-Alder systems that clearly demonstrate the degree of control over equilibrium available through substituent entropy effects. These results are of importance as regards subsequent systematic identification of Diels-Alder reactions having ideal thermochemical and physical properties.

Lenz, T.G.; Hegedus, L.S.; Vaughan, J.D.

1983-05-01

196

Extraction of chemical structures and reactions from the literature  

E-print Network

................................................................................................................................ 193 Appendix C ................................................................................................................................ 194 XIII Glossary AST = Abstract Syntax Tree CAS = Chemical Abstracts Service ChEBI = Chemical...

Lowe, Daniel Mark

2012-10-09

197

Femtosecond Chemically Activated Reactions: Concept of Nonstatistical Activation at High Thermal Energies  

E-print Network

Femtosecond chemical activation of reactions at very high thermal energies, much above the bond energyFemtosecond Chemically Activated Reactions: Concept of Nonstatistical Activation at High Thermal Energies Sang Kyu Kim, Ju Guo, J. Spencer Baskin, and Ahmed H. Zewail* Arthur Amos Noyes Chemical Physics

Kim, Sang Kyu

198

Numerical solutions of several reflected shock-wave flow fields with nonequilibrium chemical reactions  

NASA Technical Reports Server (NTRS)

The method of characteristics for a chemically reacting gas is used in the construction of the time-dependent, one-dimensional flow field resulting from the normal reflection of an incident shock wave at the end wall of a shock tube. Nonequilibrium chemical reactions are allowed behind both the incident and reflected shock waves. All the solutions are evaluated for oxygen, but the results are generally representative of any inviscid, nonconducting, and nonradiating diatomic gas. The solutions clearly show that: (1) both the incident- and reflected-shock chemical relaxation times are important in governing the time to attain steady state thermodynamic properties; and (2) adjacent to the end wall, an excess-entropy layer develops wherein the steady state values of all the thermodynamic variables except pressure differ significantly from their corresponding Rankine-Hugoniot equilibrium values.

Hanson, R. K.; Presley, L. L.; Williams, E. V.

1972-01-01

199

No electron left behind: a rule-based expert system to predict chemical reactions and reaction mechanisms  

PubMed Central

Predicting the course and major products of arbitrary reactions is a fundamental problem in chemistry, one that chemists must address in a variety of tasks ranging from synthesis design to reaction discovery. Described here is an expert system to predict organic chemical reactions based on a knowledge base of over 1,500 manually composed reaction transformation rules. Novel rule extensions are introduced to enable robust predictions and describe detailed reaction mechanisms at the level of electron flows in elementary reaction steps, ensuring that all reactions are properly balanced and atom-mapped. The core reaction prediction functionalities of this expert system are illustrated with applications including: (1) prediction of detailed reaction mechanisms; (2) computer-based learning in organic chemistry; (3) retro synthetic analysis; and (4) combinatorial library design. Select applications available via http://cdb.ics.uci.edu. PMID:19719121

Chen, Jonathan H.; Baldi, Pierre

2009-01-01

200

Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by  

E-print Network

Enzyme catalysis Enzyme catalysis is the catalysis of chemical reactions by specialized proteins known as enzymes. Catalysis of biochemical reactions in the cell is vital due to the very low reaction rates of the uncatalysed reactions. The mechanism of enzyme catalysis is similar in principle to other

Cavanagh, John

201

Progress in an oxygen-carrier reaction kinetics experiment for rotary-bed chemical looping combustion  

E-print Network

The design process for an experimental platform measuring reaction kinetics in a chemical looping combustion (CLC) process is documented and justified. To enable an experiment designed to characterize the reaction kinetics ...

Jester-Weinstein, Jack (Jack L.)

2013-01-01

202

Measurements and analysis of alpha-induced reactions of importance for nuclear astrophysics  

NASA Astrophysics Data System (ADS)

Reactions during stellar helium burning are of primary importance for understanding nucleosynthesis. A detailed understanding of the critical reaction chain 4He(2alpha, gamma)12C( alpha, gamma)16O(alpha, gamma) 20Ne is necessary both because it is the primary energy source and because it determines the ratio of 12C to 16O produced, which in turn significantly effects subsequent nucleosynthesis. Also during Helium burning, the reactions 22Ne(alpha, n)25Mg and 22Ne(alpha, gamma )26Mg are crucial in determining the amount of neutrons available for the astrophysical s-process. This thesis presents new experimental results concerning the 16O(alpha, gamma) 20Ne, 22Ne(alpha, n)25Mg, and 22Ne(alpha, gamma)26Mg reaction rates. These results are then applied to the calculation of the associated stellar reaction rates in order to achieve better accuracy.

de Messieres, Genevieve Escande

2011-11-01

203

Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle  

NASA Technical Reports Server (NTRS)

The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

Fegley, Bruce, Jr.

1997-01-01

204

Final Technical Report "Energy Partitioning in Elementary Chemical Reactions"  

SciTech Connect

This is the final technical report of the subject grant. It describes the scientific results obtained during the reporting period. These results are focused on the reactions of atomic oxygen with terminal alkenes. We have studied the production of vinoxy in these reactions. We have characterized the energy disposal in the reactions and have elaborated the reaction mechanism.

Richard Bersohn (deceased); James J. Valentini (reporting investigator)

2005-10-03

205

Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy-dependent unimolecular reaction  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Internal energy transfer and an energy a direct Monte Carlo simulation of an energy-dependent t&molecular reaction system of the type A+ B can be treated by Monte Carlo simulations. One of the most useful methods is Bird's direct simulation

Anderson, James B.

206

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2004) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a procedure to speed up the training of NPCA. The developed procedure is based on the non-parametric statistical technique of kernel smoothing. When this smoothing technique is implemented as a Neural Network, It is know as Generalized Regression Neural Network (GRNN). We present results of implementing GRNN on a test problem. In addition, we present results of an in house developed 2-D CFD code that will be used through out the project period.

Nelson Butuk

2004-12-01

207

Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks  

SciTech Connect

This is an annual technical report for the work done over the last year (period ending 9/30/2005) on the project titled ''Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks''. The aim of the project is to develop an efficient chemistry model for combustion simulations. The reduced chemistry model will be developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) will be used via a new network topology know as Non-linear Principal Components Analysis (NPCA). We report on the development of a novel procedure to speed up the training of NPCA. The same procedure termed L{sub 2}Boost can be used to increase the order of approximation of the Generalized Regression Neural Network (GRNN). It is pointed out that GRNN is a basic procedure for the emerging mesh free CFD. Also reported is an efficient simple approach of computing the derivatives of GRNN function approximation using complex variables or the Complex Step Method (CSM). The results presented demonstrate the significance of the methods developed and will be useful in many areas of applied science and engineering.

Nelson Butuk

2005-12-01

208

Chemical reactions between Venus' surface and atmosphere - An update. (Invited)  

NASA Astrophysics Data System (ADS)

The surface of Venus, at ~740K, is hot enough to allow relatively rapid chemical reactions between it and the atmosphere, i.e. weathering. Venus chemical weathering has been explored in detail [1], to the limits of available data. New data from Venus Express (VEx) and new ideas from exoplanets have sparked a modest renewal of interest in Venus weathering. Venus' surface cannot be observed in visible light, but there are several NIR ';windows' through its atmosphere that allow surface imaging. The VIRTIS spectrometer on VEx viewed the surface through one window [2]; emissivity variations among lava flows on Imdr and Themis Regios have been explained as varying degrees of weathering, and thus age [3]. The VMC camera on VEx also provides images through a NIR window, which suggest variable degrees of weathering on some basaltic plains [4]. Indirect evidence for weathering may come from varying SO2 abundance at Venus' cloud tops; repeated rapid increases and gradual declines may represent volcanic eruptions followed by weathering to form sulfate minerals [5]. Continued geochemical modeling relevant to Venus weathering is motivated by expolanet studies [6]. Models have been extended to hypothetical exo-Venuses of different temperatures and surface compositions [7]. The idea that Venus' atmosphere composition can be buffered by reaction with its surface was explored in detail, and the derived constraint extended to other types of planets [8]. Several laboratories are investigating Venus weathering, motivated in part by the hope that they can provide real constraints on timescales of Venus volcanism [3]. Aveline et al. [9] are extending early studies [10] by reacting rocks and minerals with concentrated SO2 (to accelerate reaction rates to allow detectability of products). Kohler et al. [11] are investigating the stability of metals and chalcogenides as possible causes of the low-emissivity surfaces at high elevations. Berger and Aigouy [12] studied rock alteration on a hypothetical early Venus with a water-rich atmosphere. Martin et al. [13] investigated the fate of weathered rock when heated (by igneous or impact events). Our understanding of Venus' geological history is stymied by a lack of data - spacecraft observations of and/or at its surface. VMC on VEx may continue to provide new data on surface emissivity, but their interpretation is inherently ambiguous. Laboratory experiments seem the most promising approach - attempting to quantify rates of weathering and thus volcanism [3], and (with luck) framing significant problems that can be directly answered by spacecraft observations. [1] Fegley B.Jr. et al. (1997) In Venus II. U. Ariz. Press. p. 591. [2] Helbert J. et al. (2008) GRL 35, L11201. [3] Smrekar S.E et al. (2010) Science 328, 605-608. [4] Basilevsky A.T. et al. (2012) Icarus 217, 434-450. [5] Marcq E. et al. (2013) Nature Geoscience 6, 25-28. [6] Kane S.R. et al. (2013) Astrophysical J. 770, L20. [7] Schaefer L. & Fegley B.Jr. (2011) Astrophysical J. 729, 6. [8] Treiman A.H. & Bullock M.A. (2012) Icarus 217, 534-541. [9] Aveline D.C. et al. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #2165. [10] Fegley B.Jr. & Prinn R.G. (1989) Nature 337, 55-58. [11] Kohler E. et al. (2012) Lunar Planet. Sci. Conf. 43, Abstr. #2749. [12] Berger G. & Aigouy T. (2011) Lunar Planet. Sci. Conf. 42, Abstr. #1660. [13] Martin A.M. et al. (2012) Earth Planet. Sci. Lett. 331-332, 291-304.

Treiman, A. H.

2013-12-01

209

Selectivity engineered phase transfer catalysis in the synthesis of fine chemicals: reactions of p-chloronitrobenzene with sodium sulphide  

Microsoft Academic Search

Synthesis of chemicals from the same starting material wherein more than one step involving complex reactions are involved can be engineered to produce selectively the desired product by minimising both the by-product formation and separation stages. Several products of industrial importance can be produced from the same starting material by choosing proper conditions and nature and number of phases. The

Ganapati D Yadav; Yogeeta B Jadhav; Sonali Sengupta

2003-01-01

210

Theoretical study on the mechanism and kinetics of acetaldehyde and hydroperoxyl radical: An important atmospheric reaction  

NASA Astrophysics Data System (ADS)

A systematic theoretical study was performed on the mechanism and kinetics of the atmospheric reaction of acetaldehyde (CH3CHO) and hydroperoxyl radical (HO2) in the gas phase. The DFT-B3LYP/6-311++G(3df,3pd) and CCSD(T)/6-311++G(d,p) methods were employed for calculations. Based on the calculations, this reaction leads to four different products through radical addition and hydrogen abstraction mechanisms which are very important in atmospheric and combustion chemistry. The favorable reaction paths begin with ?-hydroxyethylperoxy radical, CH3CH(OO)OH, in a exothermic process and finally leads to the product P1 (CH3COOH + OH). The overall rate constants for favorite reaction paths have been calculated at different temperatures (200-2500 K).

Farnia, Solaleh; Vahedpour, Morteza; Abedi, Mostafa; Farrokhpour, Hossein

2013-09-01

211

Heat-Of-Reaction Chemical Heat Pumps--Possible Configurations  

E-print Network

, forming a new solid. This reaction is exothermic and conducted at required process temperature, with heat being rejected to 'the load. Regeneration is accomplished by operating at reduced system pressure. The reaction with A and C is reversed, with C...-vapor reversible reaction heat pump and heat engine Heat pumps involving reactions of metal hydrides and hydrogen are of this class and have been the subject of considerable investigation for cryogenic refrigeration (15) and heat pumping. Argonne National...

Kirol, L. D.

212

Students Evaluating Teachers: Exploring the Importance of Faculty Reaction to Feedback on Teaching  

ERIC Educational Resources Information Center

This study investigates university teachers' perceptions of and reaction to students' structured feedback on various aspects of their teaching. It begins by reviewing the literature on student evaluations of teaching and on the important issues associated with performance feedback in general. Using semi-structured qualitative data gathered from a…

Moore, Sarah; Kuol, Nyiel

2005-01-01

213

Detection of a wide range of medically important fungi by the polymerase chain reaction  

Microsoft Academic Search

Summary. A polymerase chain reaction (PCR) method was developed that was capable of detecting a wide range of medically important fungi from clinical specimens. The primer pair was designed in conserved sequences of 1 8s-ribosomal RNA genes shared by most fungi. The lower limit of detection of this PCR technique was 1 pg of Cundidu ulbicans genomic DNA by ethidium

K. Makimura; SOMAY Y. MURAYAMA; H. Yamaguchi

1994-01-01

214

Verification of chemical reaction rate models in turbulent reacting flows at Schmidt number considerably exceeding 1  

Microsoft Academic Search

Relations widely used in numerical modeling describing the average rate of a chemical reaction have been analyzed. The spontaneous\\u000a distributions of the mixture fraction and reaction products measured simultaneously in different cross-sections of the jet\\u000a mixer under turbulent mixing of chemically reacting incompressible liquid media served as the basis for verification.

A. D. Chornyi; V. L. Zhdanov

2010-01-01

215

Acid-Base Chemistry According to Robert Boyle: Chemical Reactions in Words as well as Symbols  

ERIC Educational Resources Information Center

Examples of acid-base reactions from Robert Boyle's "The Sceptical Chemist" are used to illustrate the rich information content of chemical equations. Boyle required lengthy passages of florid language to describe the same reaction that can be done quite simply with a chemical equation. Reading or hearing the words, however, enriches the student's…

Goodney, David E.

2006-01-01

216

Design criteria for extraction with chemical reaction and liquid membrane permeation  

NASA Technical Reports Server (NTRS)

The design criteria for heterogeneous chemical reactions in liquid/liquid systems formally correspond to those of classical physical extraction. More complex models are presented which describe the material exchange at the individual droplets in an extraction with chemical reaction and in liquid membrane permeation.

Bart, H. J.; Bauer, A.; Lorbach, D.; Marr, R.

1988-01-01

217

Effect of gravity field on the nonequilibrium\\/nonlinear chemical oscillation reactions  

Microsoft Academic Search

Biological systems have evolved for a long time under the normal gravity. The Belousov-Zhabotinsky (BZ) reaction is a nonlinear chemical system far from the equilibrium that may be considered as a simplified chemical model of the biological systems so as to study the effect of gravity. The reaction solution is comprised of bromate in sulfuric acid as an oxidizing agent,

S. Fujieda; Y. Mori; A. Nakazawa; Y. Mogami

2001-01-01

218

Temperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott  

E-print Network

oscillations in mRNA and protein levels, the question of how to construct a network of chemical reactionsTemperature-compensated chemical reactions Kanaka Rajan and L. F. Abbott Center for Neurobiology Received 21 September 2006; published 23 February 2007 Circadian rhythms are daily oscillations

Columbia University

219

STRAIN-INDUCED STRUCTURAL CHANGES AND CHEMICAL REACTIONSII. MODELLING OF REACTIONS  

E-print Network

STRAIN-INDUCED STRUCTURAL CHANGES AND CHEMICAL REACTIONSÐII. MODELLING OF REACTIONS IN SHEAR BAND V 1997; accepted in revised form 26 April 1998) AbstractÐThe problem on strain-induced chemical reaction (SICR) and structural changes (SCs) in a thin layer inside the shear band is formulated and solved

Meyers, Marc A.

220

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels  

E-print Network

Detailed chemical kinetic reaction mechanisms for soy and rapeseed biodiesel fuels C.K. Westbrooka chemical kinetic reaction mechanism is developed for the five major components of soy biodiesel and rapeseed biodiesel fuels. These components, methyl stearate, methyl oleate, methyl linoleate, methyl

Paris-Sud XI, Université de

221

CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA  

EPA Science Inventory

The chemical research during the last decade has witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into ...

222

Studies in photochemical smog chemistry. 1. Atmospheric chemistry of toulene. 2. Analysis of chemical reaction mechanisms for photochemical smog  

SciTech Connect

This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. An experimental effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene is described. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths. A theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation.

Leone, J.A.

1985-01-01

223

Chemical reactions of ultracold alkali dimers in the lowest-energy $^3\\Sigma$ state  

E-print Network

We show that the interaction of polar alkali dimers in the quintet spin state leads to the formation of a deeply bound reaction complex. The reaction complex can decompose adiabatically into homonuclear alkali dimers (for all molecules except KRb) and into alkali trimers (for all molecules). We show that there are no barriers for these chemical reactions. This means that all alkali dimers in the $a^3\\Sigma^+$ state are chemically unstable at ultracold temperature, and the use of an optical lattice to segregate the molecules and suppress losses may be necessary. In addition, we calculate the minimum energy path for the chemical reactions of alkali hydrides. We find that the reaction of two molecules is accelerated by a strong attraction between the alkali atoms, leading to a barrierless process that produces hydrogen atoms with large kinetic energy. We discuss the unique features of the chemical reactions of ultracold alkali dimers in the $a^3\\Sigma^+$ electronic state.

Tomza, Micha?; Moszynski, Robert; Krems, Roman V

2013-01-01

224

Chemical Diffusivity and Wave Propagation in Surface Reactions: Analysis of the Bistable Monomer-Dimer Reaction Model  

NASA Astrophysics Data System (ADS)

Spatial pattern formation and wave propagation in surface reactions is controlled in part by chemical diffusion of the adsorbed reactant species. While in the simplest treatment, the chemical diffusion coefficients are taken as constant, the diffusion of one species is in fact influenced by the presence of coadsorbed species(M. Tammaro, M. Sabella, and J.W. Evans, J. Chem. Phys. 103 (1995) 10277; M. Tammaro and J.W. Evans, J. Chem. Phys. (submitted)). We thus develop an appropriate theory for chemical diffusion in mixed adlayers of mobile species. This theory is used to analyze the propagation of chemical waves associated with the displacement of the CO-poisoned state by a reactive steady state in the monomer-dimer model for CO-oxidation. We find good agreement between "exact" simulation results and those obtained from reaction-diffusion equations incorporating an appropriate description of the non-linear chemical diffusion.

Tammaro, M.; Evans, J. W.

1997-03-01

225

Phase and chemical equilibria in the transesterification reaction of vegetable oils with supercritical lower alcohols  

NASA Astrophysics Data System (ADS)

Calculations of thermodynamic data are performed for fatty acid triglycerides, free fatty acids, and fatty acid methyl esters, participants of the transesterification reaction of vegetable oils that occurs in methanol. Using the obtained thermodynamic parameters, the phase diagrams for the reaction mixture are constructed, and the chemical equilibria of the esterification reaction of free fatty acids and the transesterification reaction of fatty acid triglycerides attained upon treatment with supercritical methanol are determined. Relying on our analysis of the obtained equilibria for the esterification reaction of fatty acids and the transesterification reaction of triglycerides attained upon treatment with lower alcohols, we select the optimum conditions for performing the reaction in practice.

Anikeev, V. I.; Stepanov, D. A.; Ermakova, A.

2011-08-01

226

SUBSTITUTION REACTIONS FOR THE DETOXIFICATION OF HAZARDOUS CHEMICALS  

EPA Science Inventory

Chemical Treatment is one of several treatment techniques used for the remediation of toxic and hazardous chemicals. Chemical treatment in this report is defined as substitution of halogens by hydrogens for the conversion of halogenated organic toxicant into its native hydrocarb...

227

On the Presence of Limit-Cycles in a Model Exothermic Chemical Reaction: Sal'nikov's Oscillator with Two Temperature-Dependent Reaction Rates  

Microsoft Academic Search

This paper investigates a model chemical reaction in which a single substance undergoes a two-stage process of decay, first producing an intermediate species and finally giving a product chemical. Each of the two stages involves only simple first-order reaction kinetics, but the governing rate parameter for each of the two reactions is temperature dependent. The reaction vessel is assumed to

Lawrence K. Forbes; Mary R. Myerscough; Brian F. Gray

1991-01-01

228

Chemical reaction model for oil and gas generation from type 1 and type 2 kerogen  

SciTech Connect

A global model for the generation of oil and gas from petroleum source rocks is presented. The model consists of 13 chemical species and 10 reactions, including an alternate-pathway mechanism for kerogen pyrolysis. Reaction rate parameters and stoichiometry coefficients determined from a variety of pyrolysis data are given for both type I and type II kerogen. Use of the chemical reaction model is illustrated for typical geologic conditions.

Braun, R.L.; Burnham, A.K.

1993-06-01

229

JASPERSE CHEM 350 TEST 2 VERSION 3 Ch. 4 The Study of Chemical Reactions  

E-print Network

the following alkyl halides in order of decreasing reactivity toward SN1/E1 reactions (from most reactive 1 toward SN2 reactions (from most reactive 1 to least reactive 4). Br Br Br I 4. Rank the bond strengthJASPERSE CHEM 350 TEST 2 VERSION 3 Ch. 4 The Study of Chemical Reactions Ch. 5 Sterochemistry Ch. 6

Jasperse, Craig P.

230

JASPERSE CHEM 341 TEST 2 VERSION 3 Ch. 5 The Study of Chemical Reactions  

E-print Network

the following alkyl halides in order of decreasing reactivity toward SN1/E1 reactions (from most reactive 1 toward SN2 reactions (from most reactive 1 to least reactive 4). Br Br Br I 4. Rank the bond strength1 JASPERSE CHEM 341 TEST 2 VERSION 3 Ch. 5 The Study of Chemical Reactions Ch. 9 Stereochemistry Ch

Jasperse, Craig P.

231

The application of reversible chemical reactions to solar thermal energy systems  

Microsoft Academic Search

It has been proposed to use reversible thermochemical reactions as a means for storing thermal energy in solar energy systems. The considered approach involves the storage of thermal energy in the form of chemicals created by endothermic reactions. In addition to the storage applications, there is also interest in applying reversible reactions to solar thermal energy transport and solar thermal

R. Mar

1980-01-01

232

A comparison of reversible chemical reactions for solar thermochemical power generation  

E-print Network

453 A comparison of reversible chemical reactions for solar thermochemical power generation O. M storage of the reaction products. A number of reactions have been proposed for solar thermochemical power to be a good choice for first generation solar thermochemical power generation. Revue Phys. Appl. 15 (1980) 453

Boyer, Edmond

233

An Integrated Model for the Differentiation of Chemical-Induced Allergic and Irritant Skin Reactions  

Microsoft Academic Search

Contact and photocontact allergic as well as irritant and photoirritant skin reactions represent a major problem in clinical dermatology and during the development of new pharmaceuticals. Furthermore, there is a lack ofin vitroandin vivoassays that provide a clear differentiation between allergic and irritant skin reactions. Here, we describe an integrated model to differentiate between chemical-induced allergic and irritant skin reactions

Bernhard Homey; Christiane von Schilling; Jörg Blümel; Hans-Christian Schuppe; Thomas Ruzicka; Hans Jürgen Ahr; Percy Lehmann; Hans-Werner Vohr

1998-01-01

234

Vicher: A Virtual Reality Based Educational Module for Chemical Reaction Engineering.  

ERIC Educational Resources Information Center

A virtual reality application for undergraduate chemical kinetics and reactor design education, Vicher (Virtual Chemical Reaction Model) was originally designed to simulate a portion of a modern chemical plant. Vicher now consists of two programs: Vicher I that models catalyst deactivation and Vicher II that models nonisothermal effects in…

Bell, John T.; Fogler, H. Scott

1996-01-01

235

Tattoo-associated skin reaction: the importance of an early diagnosis and proper treatment.  

PubMed

Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea). Next to these inflammatory skin reactions we have to consider also the possibility of the development of cutaneous conditions such as pseudolymphomatous reactions and pseudoepitheliomatous hyperplasia. The aim of this study is to underline the importance of an early diagnosis by performing a histological examination especially when we are in front of suspected papulonodular lesions arising from a tattoo, followed by a proper treatment, since cutaneous neoplastic evolution is known to be a rare but possible complication. PMID:25147796

Bassi, Andrea; Campolmi, Piero; Cannarozzo, Giovanni; Conti, Rossana; Bruscino, Nicola; Gola, Massimo; Ermini, Stefano; Massi, Daniela; Moretti, Silvia

2014-01-01

236

Tattoo-Associated Skin Reaction: The Importance of an Early Diagnosis and Proper Treatment  

PubMed Central

Tattoo is going to be a very common practice especially among young people and we are witnessing a gradual increase of numerous potential complications to tattoo placement which are often seen by physicians, but generally unknown to the public. The most common skin reactions to tattoo include a transient acute inflammatory reaction due to trauma of the skin with needles and medical complications such as superficial and deep local infections, systemic infections, allergic contact dermatitis, photodermatitis, granulomatous and lichenoid reactions, and skin diseases localized on tattooed area (eczema, psoriasis, lichen, and morphea). Next to these inflammatory skin reactions we have to consider also the possibility of the development of cutaneous conditions such as pseudolymphomatous reactions and pseudoepitheliomatous hyperplasia. The aim of this study is to underline the importance of an early diagnosis by performing a histological examination especially when we are in front of suspected papulonodular lesions arising from a tattoo, followed by a proper treatment, since cutaneous neoplastic evolution is known to be a rare but possible complication. PMID:25147796

Bassi, Andrea; Campolmi, Piero; Cannarozzo, Giovanni; Conti, Rossana; Bruscino, Nicola; Gola, Massimo; Ermini, Stefano; Massi, Daniela; Moretti, Silvia

2014-01-01

237

Real World of Industrial Chemistry: Ethylene: The Organic Chemical Industry's Most Important Building Block.  

ERIC Educational Resources Information Center

The value of ethylene, as the organic chemical industry's most important building block, is discussed. The discussion focuses on the source of ethylene, its various forms and functions, and the ways in which the forms are made. (SA)

Fernelius, W. Conrad, Ed.; And Others

1979-01-01

238

A FLUID MECHANICAL APPROACH TO TURBULENT MIXING AND CHEMICAL REACTION PART I INADEQUACIES OF AVAILABLE METHODS  

Microsoft Academic Search

The series treats the mixing on the molecular scale (micromixing) of two miscible streams to bring about reaction between their constituents. The case where mixing and reaction have similar time constants is particularly interesting, although the framework is also valid for slow and instantaneous reactions. The case of fast reactions is important because no generally valid modelling is yet available,

J. BALDYGA; J. R. BOURNE

1984-01-01

239

A lattice gas automata model for heterogeneous chemical reactions at mineral surfaces and in pore networks  

SciTech Connect

A lattice gas automata (LGA) model is described, which couples solute transport with chemical reactions at mineral surfaces and in pore networks. Chemical reactions and transport are integrated into a FHP-I LGA code as a module so that the approach is readily transportable to other codes. Diffusion in a box calculations are compared to finite element Fickian diffusion results and provide an approach to quantifying space-time ratios of the models. Chemical reactions at solid surfaces, including precipitation/dissolution, sorption, and catalytic reaction, can be examined with the model because solute diffusion and mineral surface processes are all treated explicitly. The simplicity and flexibility of the LGA approach provides the ability to study the interrelationship between fluid flow and chemical reactions in porous materials, at a level of complexity that has not previously been computationally possible. 20 refs., 8 figs.

Wells, J.T. (Washington Univ., Seattle, WA (USA). Dept. of Geological Sciences); Janecky, D.R.; Travis, B.J. (Los Alamos National Lab., NM (USA))

1990-01-15

240

Molecule-based approach for computing chemical-reaction rates in upper atmosphere hypersonic flows.  

SciTech Connect

This report summarizes the work completed during FY2009 for the LDRD project 09-1332 'Molecule-Based Approach for Computing Chemical-Reaction Rates in Upper-Atmosphere Hypersonic Flows'. The goal of this project was to apply a recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary nonequilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological non-equilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, the difference between the two models can exceed 10 orders of magnitude. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates. Extensions of the model to reactions typically found in combustion flows and ionizing reactions are also found to be in very good agreement with available measurements, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

2009-08-01

241

Control of Mass Transport and Chemical Reaction Kinetics in Ultrasmall Volumes  

NASA Astrophysics Data System (ADS)

This talk will describe means for triggering chemical reactions for studying reaction kinetics under extreme confinement with sub-millisecond temporal resolution, including on-demand generation and fusion of femtoliter (10-15 L) volume water-in-oil droplets, and triggering reactions in femtoliter chambers microfabricated in poly(dimethylsiloxane) (PDMS). We demonstrated a reversible chemical toggle switch, which lays the groundwork for exploring more complex chemical and biochemical reaction sequences triggered and monitored in real time in discrete ultrasmall reactors, such as sequential and coupled enzymatic reactions. We are also developing methods to vary confinement and macromolecular crowding in ultrasmall, water-in-oil droplets and chambers micromolded in PDMS as biomimetic reaction vessels containing minimal synthetic gene circuits, in order to better understand how confinement, reduced dimensionality and macromolecular crowding affect molecular mechanisms involved in the operation and regulation of genetic circuits in living cells.

Collier, Charles

2012-02-01

242

Understanding chemical binding using the Berlin function and the reaction force  

NASA Astrophysics Data System (ADS)

We use the derivative of the electron density with respect to the reaction coordinate, interpreted through the Berlin binding function, to identify portions of the reaction path where chemical bonds are breaking and forming. The results agree with the conventional description for SN2 reactions, but they are much more general and can be used to elucidate other types of reactions also. Our analysis offers support for, and detailed information about, the use of the reaction force profile to separate the reaction coordinates into intervals, each with characteristic extents of geometry change and electronic rearrangement.

Chakraborty, Debajit; Cárdenas, Carlos; Echegaray, Eleonora; Toro-Labbe, Alejandro; Ayers, Paul W.

2012-06-01

243

A simple model for two competing chemical reactions  

NASA Astrophysics Data System (ADS)

We study a competitive reaction model in one dimension with different reactivity weights for the reactions. We consider the A + A ? A2 auto-catalytic reaction model and the A + B ? AB monomer-monomer reaction model, where A and B are monomers arriving at the surface with probabilities yA and yB, respectively. The model is studied in the site and pair mean field approximations, and by Monte Carlo simulations. The phase diagram of the model displays a line of continuous phase transitions between active and poisoned states, and we determined the critical exponents, ? and ?? of the model. Our results indicate that the critical behavior of the model does not change with the reactivity rate, and it belongs to the directed percolation universality class.

da Costa, E. C.; Figueiredo, W.

2005-12-01

244

Study of chemical reactions under the influence of ultrasound  

SciTech Connect

At Los Alamos the author is interested in sonochemistry because there is potential for accelerating reactions involving the synthesis of certain nitro compounds and for reducing the possibility of decomposition under milder reaction conditions. The author has initiated the study of the nitration of 2,4-dihydro-3H-1,2,4-triazol-3-one with concentrated nitric acid under sonication. The preparation of 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine, and oxidation of 3,6-diamino-1,2,4,5-tetrazine were also studied. Sonication reaction conditions and results of these reactions under ultrasound are discussed in detail.

Lee, Kien-Yin

1993-07-01

245

Study of chemical reactions under the influence of ultrasound  

SciTech Connect

At Los Alamos the author is interested in sonochemistry because there is potential for accelerating reactions involving the synthesis of certain nitro compounds and for reducing the possibility of decomposition under milder reaction conditions. The author has initiated the study of the nitration of 2,4-dihydro-3H-1,2,4-triazol-3-one with concentrated nitric acid under sonication. The preparation of 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine, and oxidation of 3,6-diamino-1,2,4,5-tetrazine were also studied. Sonication reaction conditions and results of these reactions under ultrasound are discussed in detail.

Lee, Kien-Yin.

1993-01-01

246

Investigation of chemical reactions in solution using API-MS  

Microsoft Academic Search

The general concepts, advantages, and applications of on-line and off-line screening to organic reaction mechanistic studies applying API-MS are reviewed. An overview is presented of the development and the present stage of connected microreactors to API ion-sources. Examples of the successful application of API in revealing, elucidating, and helping to consolidate several proposed mechanisms of organic reactions are summarized. Finally,

Leonardo Silva Santos; Larissa Knaack; Jürgen O. Metzger

2005-01-01

247

From elementary reactions to evaluated chemical mechanisms for combustion models  

Microsoft Academic Search

Methods of determining rate data for elementary reactions for combustion applications, using experimental and theoretical methods, are briefly reviewed. The approaches are illustrated by reference to recent research in three areas: (i) reactions of OH with C2H4 and C2H2, where theory, tuned by reference to experiment, has provided a substantial contribution to the determination of rate data for these complex

Michael J. Pilling

2009-01-01

248

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle  

NASA Technical Reports Server (NTRS)

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Fegley, Bruce, Jr.

1988-01-01

249

Modeling the Dynamics of Chemical Reactions Involving Multidimensional Tunneling  

NASA Astrophysics Data System (ADS)

The direct dynamics approach is employed to study prototype reactions including hydrogen and hydride transfer. The dynamics are treated with variational transition state theory including multidimensional semiclassical tunneling corrections, and the force field is modeled with semiempirical molecular orbital theory. The primary kinetic isotope effect for the (1,5) sigmatropic rearrangement reaction of cis-1,3-pentadiene is predicted and compared to experiment. The force field is obtained by molecular orbital theory with the AM1, PM3, and MINDO/3 parameterizations. The kinetic isotope effects calculated with the MINDO/3 and PM3 Hamiltonians agree with those calculated by AM1 within 13%, and the latter agree with experiment within 13%. The tunneling contributions to the kinetic isotope effects are analyzed, and the nature of the vibrationally assisted tunneling process is elucidated. The kinetic isotope effects of the reactions of CF_3 with CD_3H are studied including all internal degrees of freedom. The force field necessary for the dynamics calculations is evaluated using the neglect of diatomic differential overlap (NDDO) molecular orbital theory with semiempirical specific -reaction parameters (SRP), which are based on the standard AM1 parameterization adjusted to improve the agreement between experiment and the calculated quantities such as the vibrational frequencies of reactants and products and the classical barrier. The kinetic isotope effects are calculated using two different SRP force fields, and they are in good agreement with the experimental measurements. The picture of the corner cutting tunneling process that emerges is discussed graphically. The two NDDO-SRP models are further used to study the hydrogen abstraction reactions of CF_3 with CH_4, CD_4, and C_2 H_6, and very good agreement with experiment is obtained. Finally, a simple model hydride transfer reaction of formic acid is investigated usine the AM1 and PM3 Hamiltonians, and the results are compared to experiment.

Liu, Yi-Ping

250

Energy storage and transport by reversible chemical reactions  

NASA Astrophysics Data System (ADS)

Reversible thermochemical reactions are one of the possibilities to store and transport high temperature heat (800 K up to 1300 K). There are open cycles and closed cycles. Some reversible systems are described, as the SO2-SO3 system. A typical example of open cycle is the reaction for water decomposition. Results of a pilot plant to verify the decomposition of sulfuric acid are described; the technological feasibility of this method for hydrogen production is shown. The possibility to use other high temperature sources, as solar energy is discussed.

Beghi, G.

251

Conceptual Design of Biorefineries Through the Synthesis of Optimal Chemical-reaction Pathways  

E-print Network

on developing new pathways while optimizing existing ones. Here, potential chemicals are added to create a superstructure, then an algorithm is run to enumerate every feasible reaction stoichiometry through a mixed integer linear program (MILP). An optimal...

Pennaz, Eric James

2011-10-21

252

EVALUATION OF CHEMICAL REACTION MECHANISMS FOR PHOTOCHEMICAL SMOG. PART 2. QUANTITATIVE EVALUATION OF THE MECHANISMS (REVISED)  

EPA Science Inventory

Six chemical reaction mechanisms for photochemical smog were analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. To perform the analysis, a counter species technique was used to determine the contributions of individual reac...

253

Reformulation and solution of the master equation for multiple-well chemical reactions.  

PubMed

We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity. PMID:24053787

Georgievskii, Yuri; Miller, James A; Burke, Michael P; Klippenstein, Stephen J

2013-11-21

254

React. Kinet. Catal. Lett., Vol. 15, No. 2,245-250 (1980) DYNAMICS OF CHEMICAL REACTIONS AND NONPHYSICAL  

E-print Network

React. Kinet. Catal. Lett., Vol. 15, No. 2,245-250 (1980) DYNAMICS OF CHEMICAL REACTIONS behavior of chemical reactions,in particular,the reasonsfor slow relaxa- tions. IIoKa3aHo, qTO 14[HdpKcaum~. Prolonged transientregimes were found experimentally in chemical reactions in greatlydifferenthomogeneous

Gorban, Alexander N.

255

Exact probability distributions of selected species in stochastic chemical reaction networks.  

PubMed

Chemical reactions are discrete, stochastic events. As such, the species' molecular numbers can be described by an associated master equation. However, handling such an equation may become difficult due to the large size of reaction networks. A commonly used approach to forecast the behaviour of reaction networks is to perform computational simulations of such systems and analyse their outcome statistically. This approach, however, might require high computational costs to provide accurate results. In this paper we opt for an analytical approach to obtain the time-dependent solution of the Chemical Master Equation for selected species in a general reaction network. When the reaction networks are composed exclusively of zeroth and first-order reactions, this analytical approach significantly alleviates the computational burden required by simulation-based methods. By building upon these analytical solutions, we analyse a general monomolecular reaction network with an arbitrary number of species to obtain the exact marginal probability distribution for selected species. Additionally, we study two particular topologies of monomolecular reaction networks, namely (i) an unbranched chain of monomolecular reactions with and without synthesis and degradation reactions and (ii) a circular chain of monomolecular reactions. We illustrate our methodology and alternative ways to use it for non-linear systems by analysing a protein autoactivation mechanism. Later, we compare the computational load required for the implementation of our results and a pure computational approach to analyse an unbranched chain of monomolecular reactions. Finally, we study calcium ions gates in the sarco/endoplasmic reticulum mediated by ryanodine receptors. PMID:25155220

López-Caamal, Fernando; Marquez-Lago, Tatiana T

2014-09-01

256

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2013 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2013-01-01

257

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

Code of Federal Regulations, 2012 CFR

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2012-01-01

258

15 CFR 713.3 - Annual declaration and reporting requirements for exports and imports of Schedule 2 chemicals.  

...for exports and imports of Schedule 2 chemicals. 713.3 Section 713.3 Commerce...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.3 Annual...

2014-01-01

259

A kinetic mechanism inducing oscillations in simple chemical reactions networks  

E-print Network

, for example, cell cycle [1], Ca+ -induced oscillations [8], glycolysis [15, 20, 14], yeast metabolic cycle [19 for this work) is given by ATP in the glycolysis pathway [20]. ATP is a cofactor in some of the reaction steps (e.g. in the step catalyzed by Hexokinase: glucose - glucose-6-phosphate) while a too high

Altafini, Claudio

260

P MATRIX PROPERTIES, INJECTIVITY AND STABILITY IN CHEMICAL REACTION SYSTEMS  

E-print Network

a class of systems consisting of reactions coupled to an external rate-dependent negative feedback process is algorithmically easy to check, and immediately implies the absence of multiple equilibria as long with some external quantity giving rise to a negative feedback process. Necessary and sufficient conditions

Banaji,. Murad

261

Cellulose Oligomers: Preparation from Cellulose Triacetate, Chemical Transformations and Reactions  

Microsoft Academic Search

Cellulose oligomers obtained by a new degradation method (pivaloylysis) are used as starting materials in organic synthesis. On the one hand these oligomers are functionalized to potent glycosyl donors, on the other hand several methods are shown to generate different types of hydroxy compounds (glycosyl acceptors). Glycosidation reactions performed with these two types of building blocks allow an access to

P. Arndt; K. Bockholt; R. Gerdes; S. Huschens; J. Pyplo; H. Redlich; K. Samm

2003-01-01

262

Theoretical studies of the dynamics of chemical reactions  

SciTech Connect

Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.

Wagner, A.F. [Argonne National Laboratory, IL (United States)

1993-12-01

263

Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals  

NASA Astrophysics Data System (ADS)

Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (? > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

2014-10-01

264

Approximate reaction rates and probabilities for a class of exothermic chemical reactions  

Microsoft Academic Search

An approximate expression for the total rate constant for certain exothermic reactions is given. The approximation can be expressed simply in terms of integrals in a region about the saddle point. More complicated procedures for computing the total probability for reaction from a given reactant state are presented. This involves solution of a set of coupled differential equations in a

Edward J. Shipsey

1975-01-01

265

Analytical Solution of Steady State Equations for Chemical Reaction Networks with Bilinear Rate Laws  

PubMed Central

True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher dimensional space. We show that the linearized version of the steady state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

Halasz, Adam M.; Lai, Hong-Jian; McCabe, Meghan M.; Radhakrishnan, Krishnan; Edwards, Jeremy S.

2014-01-01

266

X-ray Microspectroscopy and Chemical Reactions in Soil Microsites  

SciTech Connect

Soils provide long-term storage of environmental contaminants, which helps to protect water and air quality and diminishes negative impacts of contaminants on human and ecosystem health. Characterizing solid-phase chemical species in highly complex matrices is essential for developing principles that can be broadly applied to the wide range of notoriously heterogeneous soils occurring at the earth's surface. In the context of historical developments in soil analytical techniques, we describe applications of bulk-sample and spatially resolved synchrotron X-ray absorption spectroscopy (XAS) for characterizing chemical species of contaminants in soils, and for determining the uniqueness of trace-element reactivity in different soil microsites. Spatially resolved X-ray techniques provide opportunities for following chemical changes within soil microsites that serve as highly localized chemical micro- (or nano-)reactors of unique composition. An example of this microreactor concept is shown for micro-X-ray absorption near edge structure analysis of metal sulfide oxidation in a contaminated soil. One research challenge is to use information and principles developed from microscale soil chemistry for predicting macroscale and field-scale behavior of soil contaminants.

D Hesterberg; M Duff; J Dixon; M Vepraskas

2011-12-31

267

EFFICIENT CHEMICAL TRANSFORMATIONS USING ALTERNATIVE REACTION CONDITIONS AND MEDIA  

EPA Science Inventory

The diverse nature of chemical entities requires various green' strategic pathways in our quest towards attaining sustainability. A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable...

268

JASPERSE CHEM 341 TEST 2 VERSION 1 Ch. 5 The Study of Chemical Reactions  

E-print Network

choice question) 4. Which of the following is true regarding an SN1 reaction? a. It would be faster at 25 an alkyl bromide and some nucleophile that you could use to make the following by SN2. (3 points) OCH2CH3 31 JASPERSE CHEM 341 TEST 2 VERSION 1 Ch. 5 The Study of Chemical Reactions Ch. 9 Stereochemistry Ch

Jasperse, Craig P.

269

Nuclear spin selection rules in chemical reactions by angular momentum algebra  

E-print Network

Nuclear spin selection rules in chemical reactions by angular momentum algebra Takeshi Oka by Quack using molecular symmetry group are derived by using angu- lar momentum algebra. Instead: Selection rules; Nuclear spin modifications; Angular momentum algebra; Ion-neutral reactions; Molecular ions

Oka, Takeshi

270

Progression in high school students (aged 16-18) conceptualizations about chemical reactions in solution  

Microsoft Academic Search

The purpose of this study was to explore the development over time of students' understandings of the concept of chemical reaction in the context of two familiar reactions in solution. The study is based on interviews of 48 students, aged 16-18, who had been successful in their year 11 examinations and had selected to study chemistry as one of their

Hong-Kwen Boo; J. R. Watson

2001-01-01

271

JASPERSE CHEM 341 TEST 2 VERSION 2 Ch. 5 The Study of Chemical Reactions  

E-print Network

A Br2, hv 8. Draw the product when the following substance undergoes E2 elimination. ("D" is deuterium1 JASPERSE CHEM 341 TEST 2 VERSION 2 Ch. 5 The Study of Chemical Reactions Ch. 9 Stereochemistry Ch. 10,11 Alkyl Halides and their Reactions: Nucleophilic Substitution and Elimination 1. Rank

Jasperse, Craig P.

272

JASPERSE CHEM 350 TEST 2 VERSION 2 Ch. 4 The Study of Chemical Reactions  

E-print Network

substance undergoes E2 elimination. ("D" is deuterium, basically just a labelled hydrogen). If the startingJASPERSE CHEM 350 TEST 2 VERSION 2 Ch. 4 The Study of Chemical Reactions Ch. 5 Sterochemistry Ch. 6 that is needed in each case) for each of the following reactions. (Minor products or inorganic side products need

Jasperse, Craig P.

273

Dimensional Reduction of the Fokker–Planck Equation for Stochastic Chemical Reactions  

Microsoft Academic Search

The Fokker-Planck equation models chemical reactions on a mesoscale. The solution is a probability density function for the copy number of the dierent molecules. The number of dimensions of the problem can be large making numerical simulation of the reactions computationally intractable. The number of dimensions is reduced here by deriving partial dierential equations for the first moments of some

LARS FERM

2006-01-01

274

Interaction between Large Vortex Structures and Chemical Reactions in Jet Flames  

Microsoft Academic Search

Microscopic structures and their dynamics shaped by vortices and chemical reactions in jet flames are investigated both numerically and experimentally in order to clarify statistical properties of combustion flows. In our direct numerical simulation with multi-step reaction mechanism of an axisymmetric jet flame, it is verified that shear vortices drifting downstream along the edges of flames make complex flame surfaces

Naoto Yokoyama; Kana Saito; Jiro Mizushima

2004-01-01

275

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination  

E-print Network

Direct Monte Carlo simulation of chemical reaction systems: Dissociation and recombination Shannon of Physics. I. INTRODUCTION In earlier studies1­5 we have found the direct Monte Carlo simulation method6 Monte Carlo simulation of dissociation-recombination reac- tions of the type M AB M A B. These reactions

Anderson, James B.

276

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors  

E-print Network

A coupled chemical burster: The chlorine dioxide-iodide reaction in two flow reactors Miles Dolnika-iodide reaction has been studied in a system consisting of two continuous flow stirred tank reactors (CSTRs). The reactors are coupled by computer monitoring of the electrochemical potential in each reactor, which

Epstein, Irving R.

277

Kinetics of endothermic decomposition reactions. I. Steady-state chemical steps  

Microsoft Academic Search

When the solid product of an endothermic decomposition reaction is porous, the rate-limiting chemical step is usually assumed to be a surface step of the gaseous product or of a precursor of that product. It is shown here that the rate of such a reaction may also depend upon rates of diffusion in the reactant phase, the rate of transfer

Alan W. Searcy; Dario Beruto

1976-01-01

278

ABIOTIC REDUCTION REACTIONS OF ANTHROPOGENIC ORGANIC CHEMICALS IN ANAEROBIC SYSTEMS: A CRITICAL REVIEW  

EPA Science Inventory

The review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural waters. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reduc...

279

Inward Propagating Chemical Waves in a Single-Phase Reaction-Diffusion System  

Microsoft Academic Search

We report our experimental and theoretical studies of inwardly propagating chemical waves (antiwaves) in a single-phase reaction-diffusion (RD) system. The experiment was conducted in an open spatial reactor using chlorite-iodide-malonic acid reaction. When the system was set to near Hopf bifurcation point, antiwaves appeared spontaneously, as predicted using both the reaction-diffusion (RD) equation and the complex Ginzburg-Landau equation (CGLE). Antiwaves

Xin Shao; Yabi Wu; Jinzhong Zhang; Hongli Wang; Qi Ouyang

2008-01-01

280

A semiclassical non-adiabatic theory for elementary chemical reactions  

E-print Network

Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom). Unlike for the standard Marcus theory, the complex amplitudes of the electronic state are chosen as reaction coordinates. Then, the dynamical equations at non vanishing temperature become those of an effective Hamiltonian submitted to damping terms and their associated Langevin random forces. The advantage of this new formalism is to extend the original theory by taking into account both ionic and covalent interactions. The standard theory is recovered only when covalent interactions are neglected. Increasing these covalent interactions from zero, the energy barrier predicted by the standard theory first depresses, next vanish (or almost vanish) and for stronger covalent interactions, covalent bond formation takes place of ET. In biochemistry, the standard Marcus theory often ...

Aubry, Serge

2014-01-01

281

Continuous chemical reaction chromatography: Progress report, December 1985--December 1988  

SciTech Connect

During the present three year project period we have been investigating continuous gas chromatographic separations, and continuous reaction gas chromatography of solid catalyzed reactions in a countercurrent moving bed. Design and construction of a computer controlled laboratory scale countercurrent moving bed apparatus was completed. In the countercurrent moving bed, a granular solid (typically 30-50 mesh) flows slowly down a vertical tube against an upflowing carrier gas. A mixture to be separated, or a reactant species, is fed continuously at an arbitrary location along the column. We have now carried out experimental investigations of separation of a binary mixture, 1,3,5-trimethylcyclohexane and 1,3,5-trimethylbenzene, and of hydrogenation in the countercurrent moving bed. 8 refs., 2 tabs.

Aris, R.; Carr, R.W.

1989-01-01

282

Influence of mineral weathering reactions on the chemical composition of soil water, springs, and ground water, Catoctin Mountains, Maryland  

USGS Publications Warehouse

During 1983 and 1984, wet precipitation was primarily a solution of dilute sulphuric acid, whereas calcium and bicarbonate were the major ions in springs and ground water in two small watersheds with a deciduous forest cover in central Maryland. Dominant ions in soil water were calcium, magnesium, and sulphate. The relative importance of mineral weathering reactions on the chemical composition of these subsurface waters was compared to the contribution from wet precipitation, biological processes, and road deicing salts. -from Author

Katz, B.G.

1989-01-01

283

A human-specific mitochondrial antibody its importance in the identification of organ-specific reactions.  

PubMed Central

A previously unrecognized autoantibody, detected by immunofluorescence, reacted with all human organs but gave negative results on tissues from rat, mouse, rabbit, guinea-pig, calf and chicken. From its predilection for mitochondria-rich cells (oncocytes) and its selective absorption with human but not animal mitochondria, it was identified as an anti-human mitochondrial antibody and named AHMA. The antibody is found in about 1% of normal subjects and is mostly of IgG class and of low titres. Its prevalence is increased in primary biliary cirrhosis where it may be associated with the standard non-species-specific AMA used for the differential diagnosis of this disease. The importance of AHMA is mainly in possible confusion with organ-specific reactions in submaxillary duct, parathyroid oxyphil cells and in trying to identify new endocrine cells such as those producing pancreatic polypeptide (HPP) in human tissues. Animals immunized with human hormones develop reactions to human mitochondria and thus produce misleading immunofluorescence reactions when used in low dilutions. PMID:330060

Swana, G T; Swana, M R; Bottazzo, G F; Doniach, D

1977-01-01

284

A human-specific mitochondrial antibody its importance in the identification of organ-specific reactions.  

PubMed

A previously unrecognized autoantibody, detected by immunofluorescence, reacted with all human organs but gave negative results on tissues from rat, mouse, rabbit, guinea-pig, calf and chicken. From its predilection for mitochondria-rich cells (oncocytes) and its selective absorption with human but not animal mitochondria, it was identified as an anti-human mitochondrial antibody and named AHMA. The antibody is found in about 1% of normal subjects and is mostly of IgG class and of low titres. Its prevalence is increased in primary biliary cirrhosis where it may be associated with the standard non-species-specific AMA used for the differential diagnosis of this disease. The importance of AHMA is mainly in possible confusion with organ-specific reactions in submaxillary duct, parathyroid oxyphil cells and in trying to identify new endocrine cells such as those producing pancreatic polypeptide (HPP) in human tissues. Animals immunized with human hormones develop reactions to human mitochondria and thus produce misleading immunofluorescence reactions when used in low dilutions. PMID:330060

Swana, G T; Swana, M R; Bottazzo, G F; Doniach, D

1977-06-01

285

Thermodynamics of coupled reactions by the amplitudes of chemical relaxation  

Microsoft Academic Search

The amplitudes of the relaxation curves, as obtained by the Temperature-jump method have been used to measure simultaneously\\u000a equilibrium constant and enthalpy for the reaction of complex formation of Ni2+ ion by 2,6-dihydroxobenzoic acid in the presence of a buffer. The experiments have been performed by changing the concentration\\u000a of metal ion at constant ligand concentration andpH as in a

F. Secco; Marcella Venturini

1994-01-01

286

Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers  

E-print Network

Effect of Finite-rate Chemical Reactions on Turbulence in Hypersonic Turbulent Boundary Layers Lian on future air-breathing hypersonic cruise vehicles will be turbulent and chemically reacting. To aid the design of such vehicles, a greater understanding of turbulent hypersonic flows is needed. Although

Martín, Pino

287

Thermal effect of chemical reactions in interactions of laser pulse with solids  

Microsoft Academic Search

The heat energy released by chemical reactions was measured in the interaction of 50-ns Nd- laser pulse with titanium, germanium, coke, and sulphur samples placed in different gas media. The samples were exposed to focused laser radiation in the intensity range of 1 - 800 MW\\/cm2. It was found that the maximum value of the ratio of released chemical energy

Anatoly Y. Vorobyov

1994-01-01

288

Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories  

Microsoft Academic Search

The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed

Nao Noguchi; Haruyuki Nakano

2009-01-01

289

WORKSHOP ON STATUS OF TEST METHODS FOR ASSESSING POTENTIAL OF CHEMICALS TO INDUCE RESPIRATORY ALLERGIC REACTIONS  

EPA Science Inventory

Because of the association between allergy and asthma and the increasing incidence of morbidity and mortality due to asthma, there is growing concern over the potential of industrial chemicals to produce allergic reactions in the respiratory tract. Two classes of chemicals have b...

290

Stochastic resonance in the absence and presence of external signals for a chemical reaction  

E-print Network

Stochastic resonance in the absence and presence of external signals for a chemical reaction Lingfa Yang, Zhonghuai Hou, and Houwen Xina) Department of Chemical Physics, University of Science random perturbation. Noise-induced oscillations and noise-induced frequency shifts have been observed

Yang, Lingfa

291

A comprehensive detailed chemical kinetic reaction mechanism for combustion of nalkane  

E-print Network

A comprehensive detailed chemical kinetic reaction mechanism for combustion of nalkane 94550, USA b University College of Ireland, Galway, Ireland Abstract Detailed chemical, published in "Combustion and Flame 156 (2008) 181-199" DOI : 10.1016/j.combustflame.2008.07.014 #12

Paris-Sud XI, Université de

292

Density functional study of chemical reaction equilibrium for dimerization reactions in slit and cylindrical nanopores  

E-print Network

and cylindrical nanopores Alexandr Malijevský1,2,a and Martin Lísal2,3 1 Department of Chemical Engineering challenges of the statistical mechanics of liquids presents a desire for reliable description of fluid con, the impact of confinement does not change only the phase behavior of a fluid but affects also its chemical

Lisal, Martin

293

KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions  

SciTech Connect

This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

Yeh, G.T.; Iskra, G.A. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil Engineering; Szecsody, J.E.; Zachara, J.M.; Streile, G.P. [Pacific Northwest Lab., Richland, WA (United States)

1995-01-01

294

Rate constants for chemical reactions in high-temperature nonequilibrium air  

NASA Technical Reports Server (NTRS)

In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

Jaffe, R. L.

1986-01-01

295

High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system  

NASA Technical Reports Server (NTRS)

An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

Jachimowski, C. J.

1975-01-01

296

RPMDRATE: Bimolecular chemical reaction rates from ring polymer molecular dynamics  

NASA Astrophysics Data System (ADS)

We present RPMDRATE, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH4, OH+CH4 and H+C2H6 reactions. Catalogue identifier: AENW_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: MIT license No. of lines in distributed program, including test data, etc.: 94512 No. of bytes in distributed program, including test data, etc.: 1395674 Distribution format: tar.gz Programming language: Fortran 90/95, Python (version 2.6.x or later, including any version of Python 3, is recommended). Computer: Not computer specific. Operating system: Any for which Python, Fortran 90/95 compiler and the required external routines are available. Has the code been vectorized or parallelized?: The program can efficiently utilize 4096+ processors, depending on problem and available computer. At low temperatures, 110 processors are reasonable for a typical umbrella integration run with an analytic potential energy function and gradients on the latest x86-64 machines.

Suleimanov, Yu. V.; Allen, J. W.; Green, W. H.

2013-03-01

297

Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level  

NASA Astrophysics Data System (ADS)

Mechanical force is a distinct and usually less explored way to activate chemical reaction because it can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free- energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force- induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: S. Garcia-Manyes, J. Liang, R. Szoszkiewicz, T-L. Kuo and J. M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

Szoszkiewicz, Robert; Garcia-Manyes, Sergi; Liang, Jian; Kuo, Tzu-Ling; Fernandez, Julio M.

2009-10-01

298

The Modification of Biocellular Chemical Reactions by Environmental Physicochemicals  

NASA Astrophysics Data System (ADS)

Environmental risk factors affect human biological system to different extent from modification of biochemical reaction to cellular catastrophe. There are considerable public concerns about electromagnetic fields and endocrine disruptors. Their risk assessments have not been fully achieved because of their scientific uncertainty: electromagnetic fields just modify the bioreaction in the restricted cells and endocrine disruptors are quite unique in that their expression is dependent on the exposure periods throughout a life. Thus, we here describe their molecular characterization to establish the new risk assessments for environmental physicochemicals.

Ishido, M.

299

The Importance of the Entropy Inequality on Numerical Simulations Using Reduced Methane-air Reaction Mechanisms  

E-print Network

Many reaction mechanisms have been developed over the past few decades to predict flame characteristics. A detailed reaction mechanism can predict flame characteristics well, but at a high computational cost. The reason for reducing reaction...

Jones, Nathan

2012-10-19

300

Theoretical Chemical Dynamics Studies of Elementary Combustion Reactions  

SciTech Connect

The objective of this research was to develop and apply methods for more accurate predictions of reaction rates based on high-level quantum chemistry. We have developed and applied efficient, robust methods for fitting global ab initio potential energy surfaces (PESs) for both spectroscopy and dynamics calculations and for performing direct dynamics simulations. Our approach addresses the problem that high-level quantum calculations are often too costly in computer time for practical applications resulting in the use of levels of theory that are often inadequate for reactions. A critical objective was to develop practical methods that require the minimum number of electronic structure calculations for acceptable fidelity to the ab initio PES. Our method does this by a procedure that determines the optimal configurations at which ab initio points are computed, and that ensures that the final fitted PES is uniformly accurate to a prescribed tolerance. Our fitting methods can be done automatically, with little or no human intervention, and with no prior knowledge of the topology of the PES. The methods are based on local fitting schemes using interpolating moving least-squares (IMLS). IMLS has advantages over the very effective modified-Shepard methods developed by Collins and others in that higher-order polynomials can be used and does not require derivatives but can benefit from them if available.

Donald L. Thompson

2009-09-30

301

Quantum chemical study of the acrolein (CH2CHCHO) + OH + O2 reactions.  

PubMed

Acrolein, a beta-unsaturated (acrylic) aldehyde, is one of the simplest multifunctional molecules, containing both alkene and aldehyde groups. Acrolein is an atmospheric pollutant formed in the photochemical oxidation of the anthropogenic VOC 1,3-butadiene, and serves as a model compound for methacrolein (MACR) and methyl vinyl ketone (MVK), the major oxidation products of the biogenic VOC isoprene. In addition, acrolein is involved in combustion and biological oxidation processes. This study presents a comprehensive theoretical analysis of the acrolein + OH + O(2) addition reactions, which is a key photochemical oxidation sequence, using the G3SX and CBS-QB3 theoretical methods. Both ab initio protocols provide relatively similar results, although the CBS-QB3 method systematically under-predicts literature heats of formation using atomization enthalpies, and also provides lower transition state barrier heights. Several new low-energy pathways for unimolecular reaction of the acrolein-OH-O(2) radicals are identified, with energy at around or below that of the acrolein-OH isomers + O(2). In each case these novel reactions have the potential to reform the hydroxyl radical (OH) and form coproducts that include glyoxal, glycolaldehyde (HOCH(2)CHO), formaldehyde (HCHO), CO, and substituted epoxides. Analogous reaction schemes are developed for the photochemical oxidation of MACR and MVK, producing a number of observed oxidation products. The reaction MACR + OH + O(2) --> hydroxyacetone + OH + CO is expected to be of particular importance. This study also proposes that O(2) addition to chemically activated acrolein-OH adducts can provide prompt regeneration of OH in the atmospheric oxidation of acrolein, via a double activation mechanism. This mechanism can also be extended to isoprene, MVK, and MACR. The importance of the novel chemistry revealed here in the atmospheric oxidation of acrolein and other structurally related OVOCs and VOCs requires further investigation. Additionally, a critical evaluation of the acrolein heat of formation is presented, and a new value of -16.7 +/- 1.0 kcal mol(-1) is recommended along with other thermochemical properties, from a W1 level calculation. PMID:20701337

Asatryan, Rubik; da Silva, Gabriel; Bozzelli, Joseph W

2010-08-19

302

Trust, but verify: On the importance of chemical structure curation in cheminformatics and QSAR modeling research  

PubMed Central

Molecular modelers and cheminformaticians typically analyze experimental data generated by other scientists. Consequently, when it comes to data accuracy, cheminformaticians are always at the mercy of data providers who may inadvertently publish (partially) erroneous data. Thus, dataset curation is crucial for any cheminformatics analysis such as similarity searching, clustering, QSAR modeling, virtual screening, etc., especially nowadays when the availability of chemical datasets in public domain has skyrocketed in recent years. Despite the obvious importance of this preliminary step in the computational analysis of any dataset, there appears to be no commonly accepted guidance or set of procedures for chemical data curation. The main objective of this paper is to emphasize the need for a standardized chemical data curation strategy that should be followed at the onset of any molecular modeling investigation. Herein, we discuss several simple but important steps for cleaning chemical records in a database including the removal of a fraction of the data that cannot be appropriately handled by conventional cheminformatics techniques. Such steps include the removal of inorganic and organometallic compounds, counterions, salts and mixtures; structure validation; ring aromatization; normalization of specific chemotypes; curation of tautomeric forms; and the deletion of duplicates. To emphasize the importance of data curation as a mandatory step in data analysis, we discuss several case studies where chemical curation of the original “raw” database enabled the successful modeling study (specifically, QSAR analysis) or resulted in a significant improvement of model's prediction accuracy. We also demonstrate that in some cases rigorously developed QSAR models could be even used to correct erroneous biological data associated with chemical compounds. We believe that good practices for curation of chemical records outlined in this paper will be of value to all scientists working in the fields of molecular modeling, cheminformatics, and QSAR studies. PMID:20572635

Fourches, Denis; Muratov, Eugene; Tropsha, Alexander

2010-01-01

303

Chemical analyses of geothermal waters and Strategic Petroleum Reserve brines for metals of economic importance  

Microsoft Academic Search

Waters from seven hydrothermal-geothermal, one geopressured-geothermal, and six Strategic Petroleum Reserve wells have been surveyed for 12 metals of economic importance using trace chemical analysis techniques. The elements sought were Cr, Co, Mn, Ta, Sn, V, Nb, Li, Sr, Pt, Au and Ag. Platinum was found at a concentration of approx. 50 ppb in a brine from the Salton Sea

J. E. Harrar; E. Raber

1984-01-01

304

Chemical reactions and fluctuations. Exact substitute processes for diffusion-reaction systems with exclusion rules  

NASA Astrophysics Data System (ADS)

Lattice systems with one species diffusion-reaction processes under local complete exclusion rules are studied analytically. We discuss a rigorously derived Fokker-Planck equation for a so-called pseudo-probability. This probability distribution depends on continuous variables in contrast to the original discrete master equation, and their stochastic dynamics may be interpreted as a substitute process which is completely equivalent to the original lattice dynamics. Especially, averages and correlation functions of the continuous variables are connected to corresponding lattice quantities by simple relations. Although the substitute process for diffusion-reaction systems with exclusion rules has some similarities to the well known substitute process for the same system without exclusion rules, their exist a set of remarkable differences. The given approach is not only valid for the discussed single species processes. We give sufficient arguments that arbitrary combinations of uni-molecular and bimolecular lattice reactions under complete local exclusions may be described in terms of our approach.

Schulz, M.

2008-07-01

305

The Unrestricted Hartree-Fock Theory of Chemical Reactions. I The Electronic Instabilities in the Chemical Reactions and the Solutions of the Unrestricted SCF LCAO MO Equation for the Homopolar Two-Center Two-Electron System  

Microsoft Academic Search

It is shown that the conventional closed shell type ground state solution of SCF LCAO MO equation, which satisfies the requirement of the symmetry, may become unstable in the course of chemical reactions. The instability of the conventional SCF ground state in the chemical reactions, is indicated for the dissociation reaction of a hydrogen molecule, the internal rotation of an

Hideo Fukutome

1972-01-01

306

Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products  

Microsoft Academic Search

The analysis of chemical warfare agents and their degradation products is an important component of verification of compliance with the Chemical Weapons Convention. Gas and liquid chromatography, particularly combined with mass spectrometry, are the major techniques used to detect and identify chemicals of concern to the Convention. The more polar analytes, and some of the more reactive or highly volatile

Robin M Black; Bob Muir

2003-01-01

307

Students' Dilemmas in Reaction Stoichiometry Problem Solving: Deducing the Limiting Reagent in Chemical Reactions  

ERIC Educational Resources Information Center

A qualitative case study was conducted to investigate the understanding of the limiting reagent concept and the strategies used by five Year 11 students when solving four reaction stoichiometry problems. Students' written problem-solving strategies were studied using the think-aloud protocol during problem-solving, and retrospective verbalisations…

Chandrasegaran, A. L.; Treagust, David F.; Waldrip, Bruce G.; Chandrasegaran, Antonia

2009-01-01

308

Analysis of turbulent free-jet hydrogen-air diffusion flames with finite chemical reaction rates  

NASA Technical Reports Server (NTRS)

A numerical analysis is presented of the nonequilibrium flow field resulting from the turbulent mixing and combustion of an axisymmetric hydrogen jet in a supersonic parallel ambient air stream. The effective turbulent transport properties are determined by means of a two-equation model of turbulence. The finite-rate chemistry model considers eight elementary reactions among six chemical species: H, O, H2O, OH, O2 and H2. The governing set of nonlinear partial differential equations was solved by using an implicit finite-difference procedure. Radial distributions were obtained at two downstream locations for some important variables affecting the flow development, such as the turbulent kinetic energy and its dissipation rate. The results show that these variables attain their peak values on the axis of symmetry. The computed distribution of velocity, temperature, and mass fractions of the chemical species gives a complete description of the flow field. The numerical predictions were compared with two sets of experimental data. Good qualitative agreement was obtained.

Sislian, J. P.; Glass, I. I.; Evans, J. S.

1979-01-01

309

Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones  

SciTech Connect

Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

Jalan, Amrit; Allen, Joshua W.; Green, William H.

2013-08-08

310

Supercritical fluid phase separations induced by chemical reactions  

SciTech Connect

Our statistical mechanical studies predict that a chemically reactive system containing species composed of C, H, N, O atoms can exhibit a phase separation into a N{sub 2}-rich and a N{sub 2}-poor phase. The preset work is concerned with the effect of the fluid phase separation upon addition of F atoms in the system. Our study shows that F atoms mainly appear as a constituent of HF in a N{sub 2}-poor fluid phase up to a certain pressure beyond which they occur as CF{sub 4} in a N{sub 2}-rich phase and that the phase separation may be abrupt in thermodynamic sense. The pressure at the phase boundary can occur at about 30 GPa at 3000 K and about 10 GPa to 20 GPa at 1000 K.Some of these ranges maybe accessible by present-day experimental high-pressure techniques. We discuss implications of this study to detonation physics.

Ree, F.H.; Viecelli, J.A.; van Thiel, M.

1997-11-01

311

Coupling quantum interpretative techniques: another look at chemical mechanisms in organic reactions  

PubMed Central

A cross ELF-NCI analysis is tested over prototypical organic reactions. The synergetic use of ELF and NCI enables the understanding of reaction mechanisms since each method can respectively identify regions of strong and weak electron pairing. Chemically intuitive results are recovered and enriched by the identification of new features. Non covalent interactions are found to foresee the evolution of the reaction from the initial steps. Within NCI, no topological catastrophe is observed as changes are continuous to such an extent that future reaction steps can be predicted from the evolution of the initial NCI critical points. Indeed, strong convergences through the reaction paths between ELF and NCI critical points enable to identify key interactions at the origin of the bond formation. VMD scripts enabling the automatic generation of movies depicting the cross NCI/ELF analysis along a reaction path (or following a Born-Oppenheimer molecular dynamics trajectory) are provided as S.I. PMID:23185140

Gillet, Natacha; Chaudret, Robin; Contreras-Garc?a, Julia; Yang, Weitao; Silvi, Bernard; Piquemal, Jean-Philip

2012-01-01

312

Coupling quantum interpretative techniques: another look at chemical mechanisms in organic reactions.  

PubMed

A cross ELF-NCI analysis is tested over prototypical organic reactions. The synergetic use of ELF and NCI enables the understanding of reaction mechanisms since each method can respectively identify regions of strong and weak electron pairing. Chemically intuitive results are recovered and enriched by the identification of new features. Non covalent interactions are found to foresee the evolution of the reaction from the initial steps. Within NCI, no topological catastrophe is observed as changes are continuous to such an extent that future reaction steps can be predicted from the evolution of the initial NCI critical points. Indeed, strong convergences through the reaction paths between ELF and NCI critical points enable to identify key interactions at the origin of the bond formation. VMD scripts enabling the automatic generation of movies depicting the cross NCI/ELF analysis along a reaction path (or following a Born-Oppenheimer molecular dynamics trajectory) are provided as S.I. PMID:23185140

Gillet, Natacha; Chaudret, Robin; Contreras-Garc?a, Julia; Yang, Weitao; Silvi, Bernard; Piquemal, Jean-Philip

2012-11-13

313

Chemical Model Systems for Cellular Nitros(yl)ation Reactions  

PubMed Central

S-nitros(yl)ation belongs to the redox-based posttranslational modifications of proteins but the underlying chemistry is controversial. In contrast to current concepts involving the autoxidation of nitric oxide (•NO, nitrogen monoxide), we and others have proposed the formation of peroxynitrite (oxoperoxonitrate(1-)) as an essential intermediate. This requires low cellular fluxes of •NO and superoxide (•O2?), for which model systems have been introduced. We here propose two new systems for nitros(yl)ation that avoid the shortcomings of previous models. Based on the thermal decomposition of 3-morpholinosydnonimine, equal fluxes of •NO and •O2? were generated and modulated by the addition of •NO donors or Cu,Zn-superoxide dismutase. As reactants for S-nitros(yl)ation, NADP+-dependent isocitrate dehydrogenase and glutathione were employed, for which optimal S-nitros(yl)ation was observed at nanomolar fluxes of •NO and •O2? at a ratio of about 3:1. The previously used reactants phenol and diaminonaphthalene, (C- and N-nitrosation) demonstrated potential participation of multiple pathways for nitros(yl)ation. According to our data, neither peroxynitrite nor autoxidation of •NO was as efficient as the 3•NO/1•O2? system in mediating S-nitros(yl)ation. In theory this could lead to an elusive nitrosonium (nitrosyl cation)-like species in the first step and to N2O3 in the subsequent reaction. Which of these two species or whether both together will participate in biological S-nitros(yl)ation remains to be elucidated. Finally, we developed several hypothetical scenarios to which the described U flux model could apply, providing conditions that allow either direct electrophilic substitution at a thiolate or S-nitros(yl)ation via transnitrosation from S-nitrosoglutathione. PMID:19477267

Daiber, Andreas; Schildknecht, Stefan; Muller, Johanna; Bachschmid, Markus M.; Ullrich, Volker

2014-01-01

314

The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research  

SciTech Connect

Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.

Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

2008-07-16

315

Calculation of total free energy yield as an alternative approach for predicting the importance of potential chemolithotrophic reactions in geothermal springs.  

PubMed

To inform hypotheses regarding the relative importance of chemolithotrophic metabolisms in geothermal environments, we calculated free energy yields of 26 chemical reactions potentially supporting chemolithotrophy in two US Great Basin hot springs, taking into account the effects of changing reactant and product activities on the Gibbs free energy as each reaction progressed. Results ranged from 1.2 × 10(-5) to 3.6 J kg(-1) spring water, or 3.7 × 10(-5) to 11.5 J s(-1) based on measured flow rates, with aerobic oxidation of CH(4) or NH4 + giving the highest average yields. Energy yields calculated without constraining pH were similar to those at constant pH except for reactions where H(+) was consumed, which often had significantly lower yields when pH was unconstrained. In contrast to the commonly used normalization of reaction chemical affinities per mole of electrons transferred, reaction energy yields for a given oxidant varied by several orders of magnitude and were more sensitive to differences in the activities of products and reactants. The high energy yield of aerobic ammonia oxidation is consistent with previous observations of significant ammonia oxidation rates and abundant ammonia-oxidizing archaea in sediments of these springs. This approach offers an additional lens through which to view the thermodynamic landscape of geothermal springs. PMID:22443686

Dodsworth, Jeremy A; McDonald, Austin I; Hedlund, Brian P

2012-08-01

316

A partial-propensity formulation of the stochastic simulation algorithm for chemical reaction networks with delays  

NASA Astrophysics Data System (ADS)

Several real-world systems, such as gene expression networks in biological cells, contain coupled chemical reactions with a time delay between reaction initiation and completion. The non-Markovian kinetics of such reaction networks can be exactly simulated using the delay stochastic simulation algorithm (dSSA). The computational cost of dSSA scales with the total number of reactions in the network. We reduce this cost to scale at most with the smaller number of species by using the concept of partial reaction propensities. The resulting delay partial-propensity direct method (dPDM) is an exact dSSA formulation for well-stirred systems of coupled chemical reactions with delays. We detail dPDM and present a theoretical analysis of its computational cost. Furthermore, we demonstrate the implications of the theoretical cost analysis in two prototypical benchmark applications. The dPDM formulation is shown to be particularly efficient for strongly coupled reaction networks, where the number of reactions is much larger than the number of species.

Ramaswamy, Rajesh; Sbalzarini, Ivo F.

2011-01-01

317

Child-Rearing Practices toward Children with Hemophilia: The Relative Importance of Clinical Characteristics and Parental Emotional Reactions.  

ERIC Educational Resources Information Center

Addresses the relative importance of clinical characteristics of the child and parental emotional reactions, to child-rearing practices towards children with hemophilia. Results indicate that mother's emotional reactions appear to have a stronger influence on child-rearing uncertainty and overprotection than clinical characteristics of the child.…

Banis, S.; Suurmeijer, Th. P. B. M.; van Peer, D. R.

1999-01-01

318

Reactions of fluorescent probes with normal and chemically modified myelin.  

PubMed

The fluorescent probes 8-anilino-1-naphthalenesulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) bind to highly purified myelin membranes obtained from bovine brain white matter. Binding of the dyes was markedly increased by environmental conditions which reduce the negative surface potential of the membrane, i.e., cations (La-3+ is greater than Ca-2+ is greater than Na-+,K-+), H-+, local anesthetics, and the antibiotic polymyxin B. Chemical alteration of accessible membrane charged groups affected dye binding in a manner consistent with the hypothesis that such binding is primarily dependent upon the membrane surface potential. Thus, binding was increased by blocking of carboxyl groups via carbodiimide activation and subsequent coupling with neutral amino acid esters, and even more so with a basic amino acid ester (e.g., arginine methyl ester). Dye binding was reduced by succinylation of amino groups, and by hydrolysis of choline and ethanolamine head groups of phospho- and sphingolipids by phospholipase C. Phospholipase C treatment of myelin, or sphingomyelin vesicles, reduced or abolished the augmentation of ANS and TNS binding due to cations, local anesthetics, or polymyxin B. Energy transfer from myelin tryptophan residues to bound ANS occurs, but with low efficiency. Oxidation of membrane tryptophan residues with N-bromosuccinimide, or alkylation with 2-hydroxy (or methoxy)-5-nitrobenzyl bromide, markedly reduced intrinsic membrane fluorescence and energy transfer to bound ANS, but did not significantly affect dye binding or the quantum yield of ANS fluorescence when excitation was at 380nm. Proteolytic digestion removed 6-30% of myelin protein, depending upon the enzyme used, but had no effect on fluorescent dye binding. It is concluded that the binding of the anionic fluorescent probes ANS and TNS to myelin is primarily a function of the membrane surface charge density and net surface potential, as is the case with other biological membranes. Conclusions about the degree of dye binding to membrane lipids or membrane proteins cannot be drawn unless additional studies are carried out on isolated water soluble membrane proteins. PMID:238581

Feinstein, M B; Felsenfeld, H

1975-07-15

319

Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions  

Microsoft Academic Search

The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature.

J. M. Schredder; T. Fujita

1984-01-01

320

Determination of riboflavin by the perturbation of active oxygen on a chemical oscillating reaction  

Microsoft Academic Search

This paper studies the perturbation of active oxygen (O2??H2O2) produced from the irradiated riboflavin on a chemical oscillating reaction, and a new and sensitive methodological approach for the determination of riboflavin is proposed based on it. An automatic experimental setup is designed to combine the irradiation of riboflavin with the analogous Belousov–Zhabotinskii reaction, which is implemented in a continuous-flow stirred

Zhang Ke; Ma Wanhong; Cai Ruxiu; Lin Zhixin; Gan Nanqin

2000-01-01

321

Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene  

Microsoft Academic Search

The influences induced by various terminal substituents and solvents on the reaction mechanism and chemical dynamics of complexing ethylene with Ni dithiolene are theoretically studied by using B3LYP method and Onsager model. It is shown that the reaction should be a two-step process, and the first step is the rate-determining step. We find that the rate constant of the rate-determining

Qing-Zhen Han; Yue-Hong Zhao; Hao Wen

2008-01-01

322

Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level  

NASA Astrophysics Data System (ADS)

Mechanical force can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free-energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule AFM force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force-induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: Sergi Garcia-Manyes, Jian Liang, Robert Szoszkiewicz, Tzu-Ling Kuo and Julio M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

Szoszkiewicz, Robert; Garcia-Manyes, Sergi; Liang, Jian; Kuo, Tzu-Ling; Fernandez, Julio M.

2010-03-01

323

Persistence of transition state structure in chemical reactions driven by fields oscillating in time  

E-print Network

Chemical reactions subjected to time-varying external forces cannot generally be described through a fixed bottleneck near the transition state barrier or dividing surface. A naive dividing surface attached to the instantaneous, but moving, barrier top also fails to be recrossing-free. We construct a moving dividing surface in phase space over a transition state trajectory. This surface is recrossing-free for both Hamiltonian and dissipative dynamics. This is confirmed even for strongly anharmonic barriers using simulation. The power of transition state theory is thereby applicable to chemical reactions and other activated processes even when the bottlenecks are time-dependent and move across space.

Galen T. Craven; Thomas Bartsch; Rigoberto Hernandez

2014-04-29

324

Chemical degradation of peptides and proteins in PLGA: a review of reactions and mechanisms.  

PubMed

Biodegradable poly(lactide-co-glycolide) (PLGA) polymers have been studied extensively for the controlled release of peptide and protein drugs. In addition to polymer biodegradation, chemical degradation of the incorporated peptide/protein has also been reported in PLGA devices, and the role of the polymer in promoting these reactions has been debated. This review summarizes the peptide/protein chemical degradation reactions that have been reported in PLGA systems and their mechanisms. Reported methods for stabilizing peptides and proteins in PLGA devices are also discussed. PMID:17828756

Houchin, M L; Topp, E M

2008-07-01

325

Journal of Chemical Ecology, Vol. 23, No. 4, 1997 REACTIONS OF Gammarus lacustris TO CHEMICAL  

E-print Network

pheromone decreases the capture efficiency of predatory larvaldragonflies (Aeshna umbrosa) (Hews, 1988 and to chemical stimuli from two types of natural predators: dragonfly larvae (Aeshna eremita) and northern pike, alarm pheromone, kairomone, predator avoidance, antipredator behavior, Esox lucius, Aeshna eremita

Wisenden, Brian D.

326

Measurement of Helical Trajectories in Chemical Reactions by Ion Imaging  

SciTech Connect

During the first year of this grant we developed methods to measure the sense of rotation of the nitric oxide molecule (NO) using a circularly polarized laser probe and with ion imaging detection. The method was applied to the measurement of the correlation of rotational angular momentum orientation with recoil direction in the photodissociation of NO{sub 2}. [''Detection of ''ended'' NO recoil in the 355 nm NO2 photodissociation mechanism'', V.K. Nestorov and J.I. Cline, J. Chem. Phys. 111, 5287-5290 (1999)]. The photodissociation work was performed at the University of Nevada with additional, partial support from NSF. In the summer of 1999 this technique was transported to and implemented at the Combustion Research Facility at Sandia National Laboratory in Livermore, CA in a study of rotationally inelastic collisions of NO molecules with Ar atoms. The summer 1999 experiments at Sandia demonstrated that it is possible to detect collision-induced rotational alignment (preferred planes of rotation) for product molecules. During the late summer and fall of 1999 the P.I. and student James Barr developed a theoretical method for quantifying the angular momentum alignment and for extracting it from ion images. During the winter and spring of 2000 (January-May) the P.I. was in residence at Sandia National Laboratory in Livermore during a sabbatical leave from the University of Nevada. During this time the P.I. collaborated with Sandia P.I. Dr. David Chandler and Sandia postdoctorals Thomas Lorenz and Elisabeth Wade in experiments measuring both rotational alignment and rotational orientation (preferred senses of rotation) in collisions of NO with Ar. Graduate student James Barr continued these experiments at Sandia through the end of June 2000. The success of our experimental techniques for measuring collisional alignment and the theoretical methods we have developed for extracting quantitative alignment parameters from ion images. Spectroscopic probing of products by resonance-enhanced multiphoton ionization (REMPI) detected by ion imaging is a powerful method for measuring the product state-resolved differential cross section (DCS) of bimolecular scattering reactions. Polarization of the REMPI probe light also makes imaging data potentially sensitive to product angular momentum polarization, as is well known from imaging studies of photodissociation. We exploit this sensitivity to obtain the state-resolved product angular momentum polarization as a function of recoil angle. Previous measurements of molecular angular momentum polarization in bimolecular scattering have either been constrained to detection in the scattering plane or have averaged around the azimuthal angle of the recoil velocity vector in the collision frame. Imaging detection captures the entire product recoil velocity sphere, enabling a more complete determination of product angular momentum polarization than is possible for experiments of lower detection dimensionality.

Cline, Joseph I.

2003-02-10

327

Modeling of multiphase flow with solidification and chemical reaction in materials processing  

NASA Astrophysics Data System (ADS)

Understanding of multiphase flow and related heat transfer and chemical reactions are the keys to increase the productivity and efficiency in industrial processes. The objective of this thesis is to utilize the computational approaches to investigate the multiphase flow and its application in the materials processes, especially in the following two areas: directional solidification, and pyrolysis and synthesis. In this thesis, numerical simulations will be performed for crystal growth of several III-V and II-VI compounds. The effects of Prandtl and Grashof numbers on the axial temperature profile, the solidification interface shape, and melt flow are investigated. For the material with high Prandtl and Grashof numbers, temperature field and growth interface will be significantly influenced by melt flow, resulting in the complicated temperature distribution and curved interface shape, so it will encounter tremendous difficulty using a traditional Bridgman growth system. A new design is proposed to reduce the melt convection. The geometric configuration of top cold and bottom hot in the melt will dramatically reduce the melt convection. The new design has been employed to simulate the melt flow and heat transfer in crystal growth with large Prandtl and Grashof numbers and the design parameters have been adjusted. Over 90% of commercial solar cells are made from silicon and directional solidification system is the one of the most important method to produce multi-crystalline silicon ingots due to its tolerance to feedstock impurities and lower manufacturing cost. A numerical model is developed to simulate the silicon ingot directional solidification process. Temperature distribution and solidification interface location are presented. Heat transfer and solidification analysis are performed to determine the energy efficiency of the silicon production furnace. Possible improvements are identified. The silicon growth process is controlled by adjusting heating power and moving the side insulation layer upward. It is possible to produce high quality crystal with a good combination of heating and cooling. SiC based ceramic materials fabricated by polymer pyrolysis and synthesis becomes a promising candidate for nuclear applications. To obtain high uniformity of microstructure/concentration fuel without crack at high operating temperature, it is important to understand transport phenomena in material processing at different scale levels. In our prior work, a system level model based on reactive porous media theory was developed to account for the pyrolysis process in uranium-ceramic nuclear fabrication In this thesis, a particle level mesoscopic model based on the Smoothed Particle Hydrodynamics (SPH) is developed for modeling the synthesis of filler U3O8 particles and SiC matrix. The system-level model provides the thermal boundary conditions needed in the particle level simulation. The evolution of particle concentration and structure as well as composition of composite produced will be investigated. Since the process temperature and heat flux play the important roles in material quality and uniformity, the effects of heating rate at different directions, filler particle size and distribution on uniformity and microstructure of the final product are investigated. Uncertainty issue is also discussed. For the multiphase flow with directional solidification, a system level based on FVM is established. In this model, melt convection, temperature distribution, phase change and solidification interface can be investigated. For the multiphase flow with chemical reaction, a particle level model based on SPH method is developed to describe the pyrolysis and synthesis process of uranium-ceramic nuclear fuel. Due to its mesh-free nature, SPH can easily handle the problems with multi phases and components, large deformation, chemical reactions and even solidifications. A multi-scale meso-macroscopic approach, which combine a mesoscopic model based on SPH method and macroscopic model based on FVM, FEM and FDM, can be applied to even more com

Wei, Jiuan

328

Ion-Molecule Reactions and Chemical Composition of Emanated from Herculane Spa Geothermal Sources  

PubMed Central

The paper presents a chemical composition analysis of the gases emanated from geothermal sources in the Herculane Spa area (Romania). The upper homologues of methane have been identified in these gases. An ion-molecule reaction mechanism could be implicated in the formation of the upper homologues of methane. The CH4+ ions that appear under the action of radiation are the starting point of these reactions. The presence of hydrogen in the emanated gases may be also a result of these reactions. PMID:19325844

Cosma, Constantin; Suciu, Ioan; Jantschi, Lorentz; Bolboaca, Sorana D.

2008-01-01

329

Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals  

NASA Astrophysics Data System (ADS)

The presence and importance of amines in the atmosphere, including aliphatic amines, continues to gain more attention. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime atmospheric chemistry. While previous studies have focused on the production of amine salts, this analysis looks at the importance of peroxy radical reactions to the formation of secondary organic aerosol. Atmospheric oxidation mechanisms are presented to explain the observed chemistry. A series of environmental chamber experiments were conducted in which aliphatic tertiary and secondary amines were reacted with either hydroxyl radical (OH) or nitrate radical (NO3). Chemical composition of the aerosol products was obtained with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Particle Into Liquid Sampler Time of Flight Mass Spectrometer (PILS-ToF-MS), while the chemical composition of the gas-phase products was obtained with a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). A number of aerosol-phase mass spectra showed highly oxidized fragments at a much higher molecular weight (MW) than the amine precursor. It is proposed that these larger compounds are oligomers formed through peroxy radical reactions with hydrogen rearrangement. Another reaction pathway observed was the formation of amine salts. The relative importance of each pathway to the overall production of aerosol is found to be dependent on the type of amine and oxidant. For example, the oligomers were observed in the tertiary methyl amines, while the formation of amine salts was more prevalent in the secondary and tertiary ethyl amines.

Price, Derek J.; Clark, Christopher H.; Tang, Xiaochen; Cocker, David R.; Purvis-Roberts, Kathleen L.; Silva, Philip J.

2014-10-01

330

Detection of chemical weapon agents and simulants using chemical ionization reaction time-of-flight mass spectrometry.  

PubMed

Chemical ionization reaction time-of-flight mass spectrometry (CIR-TOF-MS) has been used for the analysis of prepared mixtures of chemical weapon agents (CWAs) sarin and sulfur mustard. Detection of the CWA simulants 2-chloroethyl ethyl sulfide, triethyl phosphate, and dimethyl methyl phosphonate has also been investigated. Chemical ionization of all the agents and simulants was shown to be possible using the CIR-TOF-MS technique with a variety of reagent ions, and the sensitivity was optimized by variation of instrument parameters. The ionization process was found to be largely unaffected by sample humidity levels, demonstrating the potential suitability of the method to a range of environmental conditions, including the analysis of CWAs in air and in the breath of exposed individuals. PMID:17894471

Cordell, Rebecca L; Willis, Kerry A; Wyche, Kevin P; Blake, Robert S; Ellis, Andrew M; Monks, Paul S

2007-11-01

331

Studies in photochemical smog chemistry. I. Atmospheric chemistry of toluene. II. Analysis of chemical reaction mechanisms for photochemical smog  

SciTech Connect

This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where the understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. Finally, a new lumped mechanism for photochemical smog is developed and tested against experimental data from two smog chamber facilities. Advantages of this mechanism relative to the existing lumped mechanisms are discussed.

Leone, J.A.

1985-01-01

332

Rubber-to-metal bonding: An investigation of chemical reactions and adhesion at the interface  

NASA Astrophysics Data System (ADS)

Adhesion of rubber to steel plays an important role in many areas of technology. However, adhesion of natural rubber (NR) to most metals is poor due to the polarity of the rubber surface. In order to obtain adhesion, the substrates are often plated with brass, which is one of the few metals that NR will adhere to. The goal of this research was to elucidate the chemistry between rubber and brass at the interface and to develop primers that could replace the brass plating. Rubber fracture and model rubber experiments were used to determine the mechanisms responsible for adhesion between rubber and brass. Plasma polymerization was used to develop acetylene primers to replace brass plating. In the rubber fracture experiments, failure surfaces from rubber/brass lap joints and single wire adhesion tests were analyzed using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR). It was concluded that a rubber boundary layer existed, which consisted of high levels of oxidation and silicon that were related to adhesion failure. The composition of this layer depended on cure cycle. Model rubber experiments were used to determine the effects of two vulcanization accelerators, N,N-dicyclohexyl-2-benzothiazole sulfenamide and N-tert-butyl-2-benzothiazole sulfenamide, on the reactions between rubber and brass. Squalene, a low molecular weight hydrocarbon was used in place of NR. The chemical reactions between rubber and brass were characterized by IR, Raman, and XPS analysis. Analysis of the brass substrates after reaction with the model rubber systems showed that stearates, copper oxide, and sulfides formed initially on the surface. This was followed by squalene deposition and polyene formation (crosslinking). The rates at which these reactions occurred depended on the accelerator. Plasma-polymerized acetylene primers were developed using a microwave reactor. It was determined that low levels of fragmentation of acetylene molecules led to good adhesion in the rubber/plasma film/steel system. Fragmentation was controlled by the processing parameters, such as pressure, power and flow ratio used in the deposition process. Rubber/steel lap joints prepared from steel adherends coated with plasma-polymerized acetylene films outperformed joints prepared from brass-plated steel adherends in tests of initial adhesion and durability of adhesion.

Bertelsen, Craig Michael

333

Context-dependent fright reactions in captive European minnows: the importance of naturalness in laboratory experiments  

PubMed

The responses of ostariophysan fish to alarm substance (Schreckstoff) have been investigated extensively in the laboratory but there have been few tests of its role under natural conditions. Furthermore, existing studies of the efficacy of Schreckstoff as an alarm substance in the wild have typically employed indirect approaches and have failed to document specific behaviour in a quantitative manner. European minnows, Phoxinus phoxinuswere exposed to Schreckstoff in small aquaria. They responded with a suite of behavioural changes that are consistent with the explanation that they perceive danger. Fish from the same population were then exposed to Schreckstoff under conditions that more closely resembled their natural habitat. Under these near-natural conditions they showed a small decrease in feeding rate and a slight increase in group size, both effects being transitory and independent of stimulus concentration. These data reveal that the ostariophysan fright reaction is context-dependent and highlight the importance of quantifying the behaviour of fish exposed to Schreckstoff under fully natural conditions. PMID:9236015

Irving; Magurran

1997-06-01

334

Importance of the Voronoi domain partition for position-jump reaction-diffusion processes on nonuniform rectilinear lattices.  

PubMed

Position-jump processes are used for the mathematical modeling of spatially extended chemical and biological systems with increasing frequency. A large subset of the literature concerning such processes is concerned with modeling the effect of stochasticity on reaction-diffusion systems. Traditionally, computational domains have been divided into regular voxels. Molecules are assumed well mixed within each of these voxels and are allowed to react with other molecules within the same voxel or to jump to neighboring voxels with predefined transition rates. For a variety of reasons implementing position-jump processes on irregular grids is becoming increasingly important. However, it is not immediately clear what form an appropriate irregular partition of the domain should take if it is to allow the derivation of mean molecular concentrations that agree with a given partial differential equation for molecular concentrations. It has been demonstrated, in one dimension, that the Voronoi domain partition is the appropriate method with which to divide the computational domain. In this Brief Report, we investigate theoretically the propriety of the Voronoi domain partition as an appropriate method to partition domains for position-jump models in higher dimensions. We also provide simulations of diffusion processes in two dimensions in order to corroborate our results. PMID:24329390

Yates, Christian A; Baker, Ruth E

2013-11-01

335

Importance of the Voronoi domain partition for position-jump reaction-diffusion processes on nonuniform rectilinear lattices  

NASA Astrophysics Data System (ADS)

Position-jump processes are used for the mathematical modeling of spatially extended chemical and biological systems with increasing frequency. A large subset of the literature concerning such processes is concerned with modeling the effect of stochasticity on reaction-diffusion systems. Traditionally, computational domains have been divided into regular voxels. Molecules are assumed well mixed within each of these voxels and are allowed to react with other molecules within the same voxel or to jump to neighboring voxels with predefined transition rates. For a variety of reasons implementing position-jump processes on irregular grids is becoming increasingly important. However, it is not immediately clear what form an appropriate irregular partition of the domain should take if it is to allow the derivation of mean molecular concentrations that agree with a given partial differential equation for molecular concentrations. It has been demonstrated, in one dimension, that the Voronoi domain partition is the appropriate method with which to divide the computational domain. In this Brief Report, we investigate theoretically the propriety of the Voronoi domain partition as an appropriate method to partition domains for position-jump models in higher dimensions. We also provide simulations of diffusion processes in two dimensions in order to corroborate our results.

Yates, Christian A.; Baker, Ruth E.

2013-11-01

336

Chemical reaction of metal-fullerene in gas phase ^  

E-print Network

Chemical reaction of metal-fullerene in gas phase ·^Masamichi Kohno1 , Shuhei·" `··ZZOE±·S ,Q·D"OEfullerenes-ray diffraction study has proven (1) that some metal-fullerenes such as Sc@C82 and Sc2@C84 that were prepared

Maruyama, Shigeo

337

Chemical reaction of metal-fullerene in gas phase (2) >Masamichi Konoa  

E-print Network

f18-068 Chemical reaction of metal-fullerene in gas phase (2) ·>Masamichi Konoa , Syuhei Inoueb.of Tokyo Since the discovery of macroscopic generation and purification procedure of fullerenes and endohedral fullerenes, the geometric structure and the formation mechanism of them has been one of the most

Maruyama, Shigeo

338

Reaction layer formation and fracture at chemically vapor deposited diamond\\/metal interfaces  

Microsoft Academic Search

Chemically vapor deposited (CVD) diamond films have been deposited by a microwave enhanced deposition process on metal substrates including titanium, tungsten, molybdenum, and copper. Boundary reaction layers formed at the interface during the growth of the CVD diamond films have been investigated for each of these systems. In these studies, the interface has been exposed by mechanically deforming the metal

Scott S. Perry; Gabor A. Somorjai

1994-01-01

339

Approximation for the enhancement factor applicable to reversible reactions of finite rate in chemically loaded solutions  

Microsoft Academic Search

A new explicit relation is proposed for the prediction of the enhancement factor for reversible reactions of finite rate in chemically loaded solutions which also allows for unequal diffusivities. The relation for the enhancement factor is not based on an approximation of the absorption process, but is derived from a similarity which can be observed between the results of the

J. A. Hogendoorn; R. D. Vas Bhat; J. A. M. Kuipers; W. P. M. van Swaaij; G. F. Versteeg

1997-01-01

340

Using Drawing Technology to Assess Students' Visualizations of Chemical Reaction Processes  

ERIC Educational Resources Information Center

In this study, we investigated how students used a drawing tool to visualize their ideas of chemical reaction processes. We interviewed 30 students using thinking-aloud and retrospective methods and provided them with a drawing tool. We identified four types of connections the students made as they used the tool: drawing on existing knowledge,…

Chang, Hsin-Yi; Quintana, Chris; Krajcik, Joseph

2014-01-01

341

Selective area growth of III-V semiconductors by chemical beam epitaxy: study of reaction mechanisms  

Microsoft Academic Search

The localized growth of III-V epitaxial structures on substrates patterned with dielectric masks provides a flexible technique for the monolithic integration of electronic and optoelectronic devices. Chemical beam epitaxy (CBE) is an attractive growth technique for use in this approach and interest has consequently focussed on the reaction mechanisms which give rise to selective area growth in CBE. In the

Graham J. Davies; P. J. Skevington; J. S. Foord; C. L. French; C. L. Levoguer

1994-01-01

342

Super-Resolution Fingerprinting Detects Chemical Reactions and Idiosyncrasies of Single DNA Pegboards  

E-print Network

Super-Resolution Fingerprinting Detects Chemical Reactions and Idiosyncrasies of Single DNA in nanoscale topography (PAINT) using site-specific DNA probes to acquire two-dimensional density maps of specific features patterned on nanoscale DNA origami pegboards. We show that PAINT has a localization

Walter, Nils G.

343

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 2  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

344

DEVELOPMENT AND TESTING OF A SURROGATE SPECIES CHEMICAL REACTION MECHANISM. VOLUME 1  

EPA Science Inventory

A photochemical reaction mechanism has been updated and extensively evaluated. The testing and refinement of the surrogate species mechanism was performed in order to create an improved chemical mechanism for the atmospheric simulation models that are used to develop ozone contro...

345

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.  

PubMed

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors. PMID:21858361

Polak, Micha; Rubinovich, Leonid

2011-10-01

346

Chemical Kinetic Reaction Mechanisms for Combustion of Hydrocarbon and Other Types of Chemical Fuels  

DOE Data Explorer

Reaction mechanisms have been tested and validated extensively through comparisons between computed results and measured data from laboratory experiments (e.g., shock tubes, laminar flames, rapid compression machines, flow reactors, stirred reactors) and from practical systems (e.g., diesel engines, spark-ignition engines, homogeneous charge, compression ignition (HCCI) engines). These kinetic models are used to examine a wide range of combustion systems.[Taken from https://www-pls.llnl.gov/?url=science_and_technology-chemistry-combustion

347

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions  

NASA Astrophysics Data System (ADS)

This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments.

Moore, C. Bradley

2007-05-01

348

Modeling pore collapse and chemical reactions in shock-loaded HMX crystals  

NASA Astrophysics Data System (ADS)

The localization of deformation in shock-loaded crystals of high explosive material leads to the formation of hot spots, which, if hot enough, initiate chemical reactions. The collapse of microscopic pores contained within a crystal is one such process that localizes energy and generates hot spots. Given the difficulty of resolving the details of pore collapse in shock compression experiments, it is useful to study the problem using direct numerical simulation. In this work, we focus on simulating the shock-induced closure of a single pore in crystalline ?-HMX using a multiphysics finite element code. To address coupled thermal-mechanical-chemical responses, the model incorporates a crystal-mechanics-based description of thermoelasto-viscoplasticity, the crystal melting behavior, and transformation kinetics for a single-step decomposition reaction. The model is applied to stress wave amplitudes of up to 11 GPa to study the details of pore collapse, energy localization, and the early stages of reaction initiation.

Austin, R. A.; Barton, N. R.; Howard, W. M.; Fried, L. E.

2014-05-01

349

Looking for chemical reaction networks exhibiting a drift along a manifold of marginally stable states.  

PubMed

I recently reported some examples of mass-action equations that have a continuous manifold of marginally stable stationary states [Brogioli, D., 2010. Marginally stable chemical systems as precursors of life. Phys. Rev. Lett. 105, 058102; Brogioli, D., 2011. Marginal stability in chemical systems and its relevance in the origin of life. Phys. Rev. E 84, 031931]. The corresponding chemical reaction networks show nonclassical effects, i.e. a violation of the mass-action equations, under the effect of the concentration fluctuations: the chemical system drifts along the marginally stable states. I proposed that this effect is potentially involved in abiogenesis. In the present paper, I analyze the mathematical properties of mass-action equations of marginally stable chemical reaction networks. The marginal stability implies that the mass-action equations obey some conservation law; I show that the mathematical properties of the conserved quantity characterize the motion along the marginally stable stationary state manifold, i.e. they allow to predict if the fluctuations give rise to a random walk or a drift under the effect of concentration fluctuations. Moreover, I show that the presence of the drift along the manifold of marginally stable stationary-states is a critical property, i.e. at least one of the reaction constants must be fine tuned in order to obtain the drift. PMID:23160143

Brogioli, Doriano

2013-02-01

350

Progress toward chemical accuracy in the computer simulation of condensed phase reactions.  

PubMed Central

We describe a procedure for the generation of chemically accurate computer-simulation models to study chemical reactions in the condensed phase. The process involves (i) the use of a coupled semiempirical quantum and classical molecular mechanics method to represent solutes and solvent, respectively; (ii) the optimization of semiempirical quantum mechanics (QM) parameters to produce a computationally efficient and chemically accurate QM model; (iii) the calibration of a quantum/classical microsolvation model using ab initio quantum theory; and (iv) the use of statistical mechanical principles and methods to simulate, on massively parallel computers, the thermodynamic properties of chemical reactions in aqueous solution. The utility of this process is demonstrated by the calculation of the enthalpy of reaction in vacuum and free energy change in aqueous solution for a proton transfer involving methanol, methoxide, imidazole, and imidazolium, which are functional groups involved with proton transfers in many biochemical systems. An optimized semiempirical QM model is produced, which results in the calculation of heats of formation of the above chemical species to within 1.0 kcal/mol (1 kcal = 4.18 kJ) of experimental values. The use of the calibrated QM and microsolvation QM/MM (molecular mechanics) models for the simulation of a proton transfer in aqueous solution gives a calculated free energy that is within 1.0 kcal/mol (12.2 calculated vs. 12.8 experimental) of a value estimated from experimental pKa values of the reacting species. PMID:11607654

Bash, P A; Ho, L L; MacKerell, A D; Levine, D; Hallstrom, P

1996-01-01

351

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- ? CH4 + H- and CH4 + F- ? CH3F + H-: Quantum chemical calculations  

NASA Astrophysics Data System (ADS)

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- ? CH4 + H- and CH4 + F- ? CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

352

Chemical kinetic analysis of hydrogen-air ignition and reaction times  

SciTech Connect

An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

Rogers, R.C.; Schexnayder, C.J. Jr.

1981-07-01

353

Effect of Chemical Reactions on the Hydrologic Properties of Fractured and Rubbelized Glass Media  

SciTech Connect

Understanding the effect of chemical reactions on the hydrologic properties of geological media, such as porosity, permeability and dispersivity, is critical to many natural and engineered sub-surface systems. Influence of glass corrosion (precipitation and dissolution) reactions on fractured and rubbelized (crushed) forms HAN28 and LAWBP1, two candidate waste glass forms for a proposed immobilized low-activity waste (ILAW) disposal facility at the Hanford, WA site, was investigated. Flow and tracer transport experiments were conducted using fractured and rubbelized forms, before and after subjecting them to corrosion using Vapor Hydration Testing (VHT) at 200o C temperature and 200 psig pressure, causing the precipitation of alteration products. Data were analyzed using analytical expressions and CXTFIT, a transport parameter optimization code, for the estimation of the hydrologic characteristics before and after VHT. It was found that glass reactions significantly influence the hydrologic properties of ILAW glass media. Hydrologic properties of rubbelized glass decreased due to precipitation reactions, whereas those of fractured glass media increased due to reaction which led to unconfined expansion of fracture aperture. The results are unique and useful to better understand the effect of chemical reactions on the hydrologic properties of fractured and rubbelized stony media in general and glass media in particular.

Saripalli, Kanaka P.; Meyer, Philip D.; Parker, Kent E.; Lindberg, Michael J.

2005-08-19

354

Chemical kinetic analysis of hydrogen-air ignition and reaction times  

NASA Technical Reports Server (NTRS)

An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

Rogers, R. C.; Schexnayder, C. J., Jr.

1981-01-01

355

Chlorination of N-methylacetamide and amide-containing pharmaceuticals. Quantum-chemical study of the reaction mechanism.  

PubMed

Chlorination of amides is of utmost importance in biochemistry and environmental chemistry. Despite the huge body of data, the mechanism of reaction between amides and hypochlorous acid in aqueous environment remains unclear. In this work, the three different reaction pathways for chlorination of N-methylacetamide by HOCl have been considered: the one-step N-chlorination of the amide, the chlorination via O-chlorinated intermediate, and the N-chlorination of the iminol intermediate. The high-level quantum chemical G3B3 composite procedure, double-hybrid B2-PLYPD, B2K-PLYP methods, and global hybrid M06-2X and BMK methods have been employed. The calculated energy barriers have been compared to the experimental value of ?G(#)298 ? 87 kJ/mol, which corresponds to reaction rate constant k(r) ? 0.0036 M(-1) s(-1). Only the mechanism in which the iminol form of N-methylacetamide reacts with HOCl is consistent (?G(#)298 = 87.3 kJ/mol at G3B3 level) with experimental results. The analogous reaction mechanism has been calculated as the most favorable pathway in the chlorination of small-sized amides and amide-containing pharmaceuticals: carbamazepine, acetaminophen, and phenytoin. We conclude that the formation of the iminol intermediate followed by its reaction with HOCl is the general mechanism of N-chlorination for a vast array of amides. PMID:24601593

Šaki?, Davor; Šonji?, Pavica; Tandari?, Tana; Vr?ek, Valerije

2014-03-27

356

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles  

Microsoft Academic Search

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized

Derek S. Liechty; Mark J. Lewis

2011-01-01

357

Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species  

NASA Technical Reports Server (NTRS)

The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

Mlynczak, Martin G.; Solomon, Susan

1991-01-01

358

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions  

DOEpatents

The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

2003-04-01

359

Direct observation of chemical reactions on single gold nanocrystals using surface plasmon spectroscopy.  

PubMed

Heterogeneous catalysts have been pivotal to the development of the modern chemical industry and are essential for catalysing many industrial reactions. However, reaction rates are different for every individual catalyst particle and depend upon each particle's morphology and size, crystal structure and composition. Measuring the rates of reaction on single nanocrystals will enable the role of catalyst structure to be quantified. Here, using surface plasmon spectroscopy, we have directly observed the kinetics of atomic deposition onto a single gold nanocrystal and also monitored electron injection and extraction during a redox reaction involving the oxidation of ascorbic acid on a gold nanocrystal surface. These results constitute the first direct measurement of the rates of redox catalysis on single nanocrystals. PMID:18838998

Novo, Carolina; Funston, Alison M; Mulvaney, Paul

2008-10-01

360

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method  

NASA Astrophysics Data System (ADS)

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape.

Cao, Youfang; Liang, Jie

2013-07-01

361

An investigation of important gas-phase reactions of nitrogenous species from the simulation of experimental measurements in combustion systems  

Microsoft Academic Search

Simulated results from a detailed elementary reaction mechanism for nitrogen-containing species in flames consisting of hydrogen, C1 or C2 fuels are presented, and compared with bulk experimental measurements of nitrogen-containing species in a variety of combustion systems including flow reactors, perfectly stirred reactors, and low pressure laminar flames. Sensitivity analysis has been employed to highlight the important reactions of nitrogenous

K. J. HUGHES; A. S. TOMLIN; E. HAMPARTSOUMIAN; W. NIMMO; I. G. ZSELY; M. UJVARI; T. TURANYI; A. R. CLAGUE; M. J. PILLING

2001-01-01

362

Quantum-state controlled chemical reactions of ultracold potassium-rubidium molecules.  

PubMed

How does a chemical reaction proceed at ultralow temperatures? Can simple quantum mechanical rules such as quantum statistics, single partial-wave scattering, and quantum threshold laws provide a clear understanding of the molecular reactivity under a vanishing collision energy? Starting with an optically trapped near-quantum-degenerate gas of polar 40K87Rb molecules prepared in their absolute ground state, we report experimental evidence for exothermic atom-exchange chemical reactions. When these fermionic molecules were prepared in a single quantum state at a temperature of a few hundred nanokelvin, we observed p-wave-dominated quantum threshold collisions arising from tunneling through an angular momentum barrier followed by a short-range chemical reaction with a probability near unity. When these molecules were prepared in two different internal states or when molecules and atoms were brought together, the reaction rates were enhanced by a factor of 10 to 100 as a result of s-wave scattering, which does not have a centrifugal barrier. The measured rates agree with predicted universal loss rates related to the two-body van der Waals length. PMID:20150499

Ospelkaus, S; Ni, K-K; Wang, D; de Miranda, M H G; Neyenhuis, B; Quéméner, G; Julienne, P S; Bohn, J L; Jin, D S; Ye, J

2010-02-12

363

Oxidation of NaBr Aerosol by Ozone and Hydroxyl Radicals: Importance of Reactions  

Microsoft Academic Search

The release of Br atoms from photolyzable bromine species is responsible for the almost complete destruction of ground-level ozone observed in the Arctic after Polar sunrise, and likely for the partial destruction of ozone observed in the marine boundary layer at mid-latitudes. Based on previous studies of the reaction of deliquesced NaCl particles with hydroxyl radicals, a surface reaction mechanism

S. W. Hunt; W. Wang; A. Laskin; D. J. Gaspar; L. M. Wingen; B. J. Finlayson-Pitts

2003-01-01

364

A combined quantum-classical dynamics method for calculating thermal rate constants of chemical reactions in solution  

E-print Network

-flux correlation function for calculating the thermal rate constants of chemical reactions in solutionA combined quantum-classical dynamics method for calculating thermal rate constants of chemical reactions in solution Thanh N. Truong,") J. Andrew McCammon, and Donald J. Kouri Department of Chemistry

Truong, Thanh N.

365

Journal of Molecular Catalysis A: Chemical 163 (2000) 189204 Catalytic reaction rates in thermodynamically non-ideal systems  

E-print Network

Journal of Molecular Catalysis A: Chemical 163 (2000) 189­204 Catalytic reaction rates in the defining equations for all relevant thermodynamic properties. Catalytic reactions in gas of Molecular Catalysis A: Chemical 163 (2000) 189­204 cracking rates on intrazeolite paraffin activities

Iglesia, Enrique

366

Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories  

NASA Astrophysics Data System (ADS)

The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed with the numbers of the ionic bonds treated as generation. A pair of VB structures is related to each other if one VB structure is transferred into the other by changing a covalent bond to an ionic bond. The former and latter VB structures are named parent and child structures, respectively. The weights of the bond pictures are computed as the sum of the CASVB occupation numbers running from the top generation to the bottom along the descent of the VB structures. Thus, a number of CASVB occupation numbers are collected into a small number of indices, and a clear bond picture may be obtained from the CASVB wave function. The scheme was applied to the hydrogen exchange reaction H2+F-->H+HF and the Diels-Alder reaction C5H6(cyclopentadiene)+CH2=CH2(ethylene)-->C7H10(norbornene). In both the reactions, the scheme gave a clear picture for the Born-Oppenheimer dynamics trajectories. The reconstruction of the bonds during reactions was well described by following the temporal changes in weight.

Noguchi, Nao; Nakano, Haruyuki

2009-04-01

367

Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide  

NASA Technical Reports Server (NTRS)

Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300 C. The oxidation kinetics were monitored using thermogravimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experiment results.

Opila, Elizabeth

1995-01-01

368

Simulations of isoprene: Ozone reactions for a general circulation/chemical transport model  

NASA Technical Reports Server (NTRS)

A parameterized reaction mechanism has been created to examine the interactions between isoprene and other tropospheric gas-phase chemicals. Tests of the parameterization have shown that its results match those of a more complex reaction set to a high degree of accuracy. Comparisons between test runs have shown that the presence of isoprene at the start of a six day interval can enhance later ozone concentrations by as much as twenty-nine percent. The test cases used no input fluxes beyond the initial time, implying that a single input of a biogenic hydrocarbon to an airmass can alter its ozone chemistry over a time scale on the order of a week.

Makar, P. A.; Mcconnell, J. C.

1994-01-01

369

Chemical accuracy in QM/MM calculations on enzyme-catalysed reactions  

PubMed Central

Combined quantum mechanics/molecular mechanics (QM/MM) modelling has the potential to answer fundamental questions about enzyme mechanisms and catalysis. Calculations using QM/MM methods can now predict barriers for enzyme-catalysed reactions with unprecedented, near chemical accuracy, i.e. to within 1 kcal/mol in the best cases. Quantitative predictions from first-principles calculations were only previously possible for very small molecules. At this level, quantitative, reliable predictions can be made about the mechanisms of enzyme-catalysed reactions. This development signals a new era of computational biochemistry. PMID:17880750

Mulholland, Adrian J

2007-01-01

370

Investigation of shock-induced and shock-assisted chemical reactions in molybdenum-silicon powder mixtures  

NASA Astrophysics Data System (ADS)

In this research, chemical reactions occurring in molybdenum and silicon powder mixtures under "shock-induced" (those occurring during the high-pressure shock state) and "shock-assisted" (those occurring subsequent to the shock event, but due to bulk temperature increases) conditions were investigated. Differences in the densities and yield strengths of the two constituents, in addition to the large heat of reaction associated with molybdenum disilicide (MoSi2) formation can lead to shock-induced as well as shock-assisted reactions, which make this an ideal system to delineate the kinetics and mechanisms of reactions occurring in shock-compressed powder mixtures. Shock recovery experiments performed on Mo + 2 Si powder mixtures employing cylindrical implosion geometry showed thermally initiated reactions. A mixed phase eutectic type microstructure of MoSi2 and Mo 5Si3, resulting from reaction occurring due to melting of both reactants, was observed in axial regions of the cylindrical compacts. In regions surrounding the mach stem, melting of only silicon and reaction occurring via dissolution and re-precipitation forming MoSi2 spherules surrounding molybdenum particles in a melted and solidified silicon matrix was observed. The planar pressure shock recovery geometry showed a single phase MoSi2, microstructure formed due to a solid-state pressure-induced reaction process. The time-resolved instrumented experiments were performed using a single stage gas gun in the velocity range of 500 m/s to 1 km/s, and employed poly-vinyl di-flouride (PVDF) stress gauges placed at the front and rear surfaces of the powder to determine the crush strength, densification history, and reaction initiation threshold conditions. Time-resolved experiments performed on ˜58% dense Mo + 2 Si powder mixtures at input stresses less than 4 GPa, showed characteristics of powder densification and dispersed propagated wave stress profiles with rise time >˜40 nanoseconds. At input stress between 4--6 GPa, the powder mixtures showed a sharp rise time (<˜10 ns) of propagated wave profile and an expanded state of products revealing conclusive evidence of shock-induced reaction. At input stresses greater than 6 GPa, the powder mixtures showed a lower rise time and transition to a low-compressibility (melt) state indicating lack of shock-induced reaction. The results of this work show that (a) premature formation of a melt phase restricts mixing between reactants and inhibits "shock-induced" reaction initiation, although "shock-assisted" reactions can still occur in time scales of thermal equilibrium, and (b) the crush strength of powder mixtures is the most important parameter that controls initiation of a "shock-induced" reaction. Reaction synthesis experiments conducted on 55--95% dense Mo + 2 Si powder mixture compacts under an applied electric field showed that SHS reactions that would have normally become extinguished without the application of electric field, were observed to be self-sustained. Under such conditions, the reaction kinetics were observed to be enhanced and the reaction products showed a highly refined microstructure.

Vandersall, Kevin Stewart

1999-10-01

371

Chemical TOPAZ: Modifications to the heat transfer code TOPAZ: The addition of chemical reaction kinetics and chemical mixtures  

SciTech Connect

This is a report describing the modifications which have been made to the heat flow code TOPAZ to allow the inclusion of thermally controlled chemical kinetics. This report is broken into parts. The first part is an introduction to the general assumptions and theoretical underpinning that were used to develop the model. The second section describes the changes that have been implemented into the code. The third section is the users manual for the input for the code. The fourth section is a compilation of hints, common errors, and things to be aware of while you are getting started. The fifth section gives a sample problem using the new code. This manual addenda is written with the presumption that most readers are not fluent with chemical concepts. Therefore, we shall in this section endeavor to describe the requirements that must be met before chemistry can occur and how we have modeled the chemistry in the code.

Nichols, A.L. III.

1990-06-07

372

Numerical simulation of the interaction of transport, diffusion and chemical reactions in an urban plume  

NASA Technical Reports Server (NTRS)

A model system is presented that takes into account the main physical and chemical processes on the regional scale here in an area of 100x100 sq km. The horizontal gridsize used is 2x2 sq km. For a case study, it is demonstrated how the model system can be used to separate the contributions of the processes advection, turbulent diffusion, and chemical reactions to the diurnal cycle of ozone. In this way, typical features which are visible in observations and are reproduced by the numerical simulations can be interpreted.

Vogel, Bernhard; Vogel, Heike; Fiedler, Franz

1994-01-01

373

Applications of the ETS-NOCV method in descriptions of chemical reactions  

Microsoft Academic Search

The present study characterizes changes in the electronic structure of reactants during chemical reactions based on the combined\\u000a charge and energy decomposition scheme, ETS-NOCV (extended transition state–natural orbitals for chemical valence). Decomposition\\u000a of the activation barrier, ?E\\u000a #, into stabilizing (orbital interaction, ?E\\u000a orb, and electrostatic, ?E\\u000a elstat) and destabilizing (Pauli repulsion, ?E\\u000a Pauli, and geometry distortion energy, ?E\\u000a dist)

Mariusz Pawe? Mitoraj; Monika Parafiniuk; Monika Srebro; Micha? Handzlik; Agnieszka Buczek; Artur Michalak

374

The Q-K model for gas-phase chemical reaction rates  

NASA Astrophysics Data System (ADS)

The quantum-kinetic, or Q-K, model is based on the quantum vibration model that is employed in the computation of gas flows at the molecular level by the direct simulation Monte Carlo (DSMC) method. The Q-K procedure for dissociation is physically realistic within the context of the vibration model in that the reaction occurs upon the selection of the vibrational level that corresponds to dissociation. An analogous, but entirely phenomenological, procedure has been presented for endothermic exchange and chain reactions. These procedures for the endothermic reactions have been well validated, but the existing procedures for the corresponding exothermic reactions have proved to be problematic. This paper presents new procedures for the exothermic reactions that are computationally efficient and provide a near exact match with the equilibrium constant of statistical mechanics. The Q-K model does not depend on the availability of continuum rate coefficients. Instead, the simplicity of the new DSMC procedures allows analytical expressions to be written down for the corresponding rate coefficients in an equilibrium gas. These are used to validate the Q-K model for reactions in high temperature air and in hydrogen-oxygen combustion. The development of the Q-K model has been driven by the need for efficient reaction procedures in DSMC applications that often involve the computation of billions of simulated collisions. It is not intended to compete with the modern theories for gas-phase chemical reactions that employ more accurate physical representations of real reactions. At the same time, the degree of validation of the model is such that the analytical expressions for the rate coefficients that correspond to the model should be useful in their own right.

Bird, G. A.

2011-10-01

375

Volume 192, number 4 CHEMICAL PHYSICS LETTERS 8 May 1992 Cumulative reaction probabilities for H + H2-+H2+ H  

E-print Network

Volume 192, number 4 CHEMICAL PHYSICS LETTERS 8 May 1992 Cumulative reaction probabilities for H probabilities. Thus coupling between the reaction mode and other modes is in- cluded in this second in this extreme case, there is reasonable agreement between the cumulative reaction probabilities calculated

Miller, William H.

376

A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction  

ERIC Educational Resources Information Center

A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

Sattsangi, Prem D.

2011-01-01

377

The new chemical biology of nitrite reactions with hemoglobin: R-state catalysis, oxidative denitrosylation, and nitrite reductase/anhydrase.  

PubMed

Because of their critical biological roles, hemoglobin and myoglobin are among the most extensively studied proteins in human history, while nitrite tops the list of most-studied small molecules. And although the reactions between them have been examined for more than 140 years, a series of unusual and critical allosterically modulated reactions have only recently been characterized. In this Account, we review three novel metal- and nitrite-catalyzed reaction pathways in the context of historical studies of nitrite and hemoglobin chemistry and attempt to place them in the biological framework of hypoxic signaling. Haldane first described the reaction between nitrite and deoxymyoglobin, forming iron-nitrosylated myoglobin, in his analysis of the meat-curing process more than a century ago. The reaction of nitrous acid with deoxyhemoglobin to form nitric oxide (NO) and methemoglobin was more fully characterized by Brooks in 1937, while the mechanism and unusual behavior of this reaction were further detailed by Doyle and colleagues in 1981. During the past decade, multiple physiological studies have surprisingly revealed that nitrite represents a biological reservoir of NO that can regulate hypoxic vasodilation, cellular respiration, and signaling. Importantly, chemical analysis of this new biology suggests a vital role for deoxyhemoglobin- and deoxymyoglobin-dependent nitrite reduction in these processes. The use of UV-vis deconvolution and electron paramagnetic resonance (EPR) spectroscopy, in addition to refined gas-phase chemiluminescent NO detection, has led to the discovery of three novel and unexpected chemistries between nitrite and deoxyhemoglobin that may contribute to and facilitate hypoxic NO generation and signaling. First, R-state, or allosteric, autocatalysis of nitrite reduction increases the rate of NO generation by deoxyhemoglobin and results in maximal NO production at approximately 50% hemoglobin oxygen saturation, which is physiologically associated with greatest NO-dependent vasodilation. Second, oxidative denitrosylation of the iron-nitrosyl product formed in the deoxyhemoglobin-nitrite reaction allows for NO formation and release in a partially oxygenated environment. Finally, the deoxyhemoglobin-nitrite reaction participates in a nitrite reductase/anhydrase redox cycle that catalyzes the anaerobic conversion of two molecules of nitrite into dinitrogen trioxide (N(2)O(3)). N(2)O(3) may then nitrosate proteins, diffuse across hydrophobic erythrocyte membrane channels such as aquaphorin or Rh, or reconstitute NO via homolysis to NO and NO(2)(*). Importantly, the nitrite reductase/anhydrase redox pathway also represents a novel mechanism of both anaerobic and metal-catalyzed N(2)O(3) formation and S-nitrosation and may thus play a vital role in NO-dependent signaling in a hypoxic and heme-rich environment. We consider how these reactions may contribute to physiological and pathological hypoxic signaling. PMID:18783254

Gladwin, Mark T; Grubina, Rozalina; Doyle, Michael P

2009-01-20

378

Cross-section studies of important neutron and relativistic deuteron reactions  

NASA Astrophysics Data System (ADS)

The cross-sections of relativistic deuteron reactions on natural copper were studied by the means of activation method. The deuteron beams produced by JINR Nuclotron (Russia) with energies from 1 GeV up to 8 GeV were used. Lack of such cross-sections prevents the usage of copper foils for beam integral monitoring. The copper monitors will help us to improve the beam integral determination during ADS studies. The yttrium samples are very suitable activation detectors for monitoring of neutron fields not only in the ADS studies. But experimental cross-section data for higher energy threshold neutron reactions are still missing. This situation is the reason why we have started to study neutron reactions on yttrium by the means of quasi mono-energetic neutron source based on NPI ?ež cyclotron (Czech Republic).

Wagner, V.; Suchopár, M.; Vrzalová, J.; Chudoba, P.; Herman, T.; Svoboda, O.; Geier, B.; Krása, A.; Majerle, M.; Kugler, A.; Adam, J.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunikov, S.; Zavorka, L.; Vladimirova, N.; Bielewicz, M.; Kilim, S.; Szuta, M.; Strugalska-Gola, E.

2014-09-01

379

Importance of the 1n-stripping process in the 6Li + 159Tb reaction  

NASA Astrophysics Data System (ADS)

The inclusive cross sections of the ? particles produced in the reaction 6Li + 159Tb have been measured at energies around the Coulomb barrier. The measured cross sections are found to be orders of magnitude larger than the calculated cross sections of 6Li breaking into ? and d fragments, thus indicating contributions from other processes. The experimental cross sections of 1n-stripping and 1n-pickup processes have been determined from an entirely different measurement, reported earlier. Apart from incomplete fusion and d-transfer processes, the 1n-stripping process is found to be a significant contributor to the inclusive ?-particle cross sections in this reaction.

Pradhan, M. K.; Mukherjee, A.; Roy, Subinit; Basu, P.; Goswami, A.; Kshetri, R.; Palit, R.; Parkar, V. V.; Ray, M.; Saha Sarkar, M.; Santra, S.

2013-12-01

380

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation.  

PubMed

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations. PMID:25034613

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E; Thiré, Nicolas; Fowe, Emmanuel P; Bisson, Éric; Hebeisen, Christoph T; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D; Sanderson, Joseph; Schuurman, Michael S; Légaré, François

2014-01-01

381

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation  

NASA Astrophysics Data System (ADS)

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266?nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel; Schmidt, Bruno E.; Thiré, Nicolas; Fowe, Emmanuel P.; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguére, Mathieu; Kieffer, Jean-Claude; Spanner, Michael; Bandrauk, André D.; Sanderson, Joseph; Schuurman, Michael S.; Légaré, François

2014-07-01

382

How green is a chemical reaction? Application of LCA to green chemistry.  

PubMed

In the present work Life Cycle Assessment (LCA) is used in order to evaluate a chemical reaction from an environmental point of view. The objective is to assess the usefulness of this methodology as an environmental tool to be applied to green chemistry. As an example, two routes of obtaining maleic anhydride are compared using LCA, to ascertain which one is the most environmentally friendly. From the results obtained in this work it can be concluded that LCA seems to be a valuable tool for the environmental assessment of a chemical reaction, because it takes into account all the life cycle stages of the process and discusses the impact of the environmental burdens inventoried according to a diversity of impact categories. PMID:12521184

Domènech, Xavier; Ayllón, José A; Peral, José; Rieradevall, Joan

2002-12-15

383

Effect of noise on chemical waves in three-dimensional reaction-diffusion systems with gradient  

Microsoft Academic Search

The effect of noise on chemical waves in a quasi-three-dimensional reaction-diffusion medium with a gradient in the third dimension is studied using the FitzHugh-Nagumo model [R. FitzHugh, Biophysics J. 1, 445 (1961)]. Numerical simulations reveal that noise of appropriate intensity can postpone the onset of turbulence and stabilize the three-dimensional (3D) waves which would otherwise undergo the gradient-induced collapse. It

Xiaochuan Lu; Chunyan Wang; Chun Qiao; Yabi Wu; Qi Ouyang; Hongli Wang

2008-01-01

384

Identification of amino acid residues important in the cyclization reactions of chalcone and stilbene synthases.  

PubMed Central

Chalcone synthase (CHS) and stilbene synthase (STS) catalyse condensation reactions of p-coumaroyl-CoA and three C(2) units from malonyl-CoA up to a common tetraketide intermediate but then catalyse different cyclization reactions to produce naringenin chalcone and resveratrol respectively. On the basis of sequence alignment with other condensing enzymes including 3-ketoacyl-(acyl carrier protein) synthases of polyketide and fatty-acid synthases, site-directed mutagenesis was performed on the active-site G(372)FGPG loops in CHS and STS. The CHS-P375G mutant showed a 6-fold decrease in overall condensing activity with selectively increased production of p-coumaroyltriacetic acid lactone (CTAL, the derailment product of the tetraketide intermediate). Meanwhile, resveratrol production by STS-P(375)G strongly decreased to give various products in the order CTAL> resveratrol approximately bisnoryangonin>naringenin. As a result, naringenin production (cross-reaction) by STS-P(375)G was close to 30% of resveratrol production. Both G(374)L mutants of CHS and STS showed no condensing activity with residual malonyl-CoA decarboxylase activity. These results suggested that the G(372)FGPG loop in CHS and STS contribute to a determination of the outcome during cyclization reactions by serving as a part of the active-site scaffold on which the stereochemistry of cyclization is performed. These observations provide the first biochemical indication that cyclization reactions are modulated by active-site geometry. The implications for the evolutionary relationship of these enzymes are also discussed. PMID:10926848

Suh, D Y; Fukuma, K; Kagami, J; Yamazaki, Y; Shibuya, M; Ebizuka, Y; Sankawa, U

2000-01-01

385

Plasmonic Properties of Bimetallic Nanostructures and Their Applications in Hydrogen Sensing and Chemical Reactions  

NASA Astrophysics Data System (ADS)

Noble metal nanocrystals have attracted great interest from a wide range of research fields because of their intriguing properties endowed by their localized surface plasmon resonances, which are the collective oscillations of free electrons. Under resonant excitation, metal nanostructures exhibit very large scattering and absorption cross sections and large near-field enhancement. These extraordinary properties can be used in different applications, such as plasmonic sensing and imaging, plasmon-controlled optics, photothermal therapy, photocatalysis, solar cells, and so on. Gold and Silver nanocrystals have plasmon resonances in the visible and near-infrared regions. However, gold and silver are not suitable for some applications. For example, they are generally inactive for catalyzing chemical reactions. The integration of plasmonic metals with other metals can offer superior or new physical/chemical properties. In this thesis, I prepared Au/Ag and Au/Pd bimetallic nanostructures and studied their plasmonic properties and applications in hydrogen sensing and photocatalysis. Seeds have a crucial importance in the synthesis of bimetallic nanostructures. I therefore first studied the roles of the crystalline structure and shape of seeds on the overgrowth of bimetallic nanostructures. The overgrowth of silver and palladium on single crystalline Au nanorods, multicrystalline Au nanorods, and nanobipyramids were studied under the same conditions for each metal. The growths of silver and palladium on single crystalline Au nanorods gave cuboidal nanostructures, while rod-shaped nanostructures were obtained from the growths of silver and palladium on multicrystalline Au nanorods and nanobipyramids. Moreover, the growths of silver and palladium on multicrystalline Au nanobipyramids started at the stepped side facets, while the growths started at the twin boundaries on multicrystalline Au nanorods. These results unambiguously indicate that the crystalline structure of seeds plays a significant role on the final morphologies of multimetallic nanostructures, while the seed shape has a prominent effect on the growth kinetics. Four plasmon resonance bands were observed in Au/Ag bimetallic nanocrystals. I then studied the evolution and nature of the four plasmon bands during the silver coating on Au nanorods both experimentally and theoretically. Electrodynamic simulations revealed that the lowest-energy peak belongs to the longitudinal dipolar plasmon mode, the second-lowest-energy peak is the transverse dipolar plasmon mode, and the two highest-energy peaks can be attributed to octupolar plasmon modes. The retardation effect and the interference between two perpendicularly polarized excitations along the edge directions are important for the formation of the distinct highest-energy and second-highest-energy octupolar plasmon modes, respectively. As the Ag shell thickness is increased, the longitudinal plasmon mode blue-shifts, the transverse plasmon mode first blue-shifts and then red-shifts slightly, and the two octupolar plasmon modes stay at nearly constant wavelengths. The extinction intensities of all the four plasmon bands increase with the increase of the overall particle size. Palladium is widely used in hydrogen sensing and catalysis. I therefore studied the applications of Au/Pd bimetallic nanostructures in hydrogen sensing and photocatalysis. Two types of Au/Pd bimetallic nanostructures, nanostructures with continuous and discontinuous Pd shells, were employed to study their hydrogen sensing performances. For the nanostructures with continuous Pd shell, the hydrogen sensing performances were improved with the increase in the Pd shell thickness. A plasmon shift of 56 nm was observed when the hydrogen concentration was 4%. The nanostructures with discontinuous Pd shell exhibited smaller plasmon shifts compared with those with continuous Pd shell. For the photocatalytic application of Au/Pd bimetallic nanostructures, I studied their photocatalytic performance for Suzuki coupling reactions. The results indicate that plasmoni

Jiang, Ruibin

386

Olfactory responses of medically and economically important mites (Acari: Epidermoptidae and Acaridae) to volatile chemicals.  

PubMed

Dermatophagoides farinae Hughes (Acari: Epidermoptidae), the American house dust mite, and Tyrophagus putrescentiae (Schrank) (Acari: Acaridae), the mold mite, are medically and economically important but controlling them has proved difficult, and recolonization is commonplace. Their behavioral responses to different sources of volatile chemicals are still not fully elucidated. For the first time, the Y-tube olfactometer, which is an enclosed bioassay to resolve responses to test and control volatiles, has been successfully used with these mites. Mites were tested individually, and both T. putrescentiae and D. farinae responded to food volatiles. Y-tube olfactometers may be used to test for potential semiochemicals, thereby increasing knowledge of our behavior of astigmatic mites. PMID:17427710

Skelton, A C; Birkett, M A; Pickett, J A; Cameron, M M

2007-03-01

387

Ab initio studies of equations of state and chemical reactions of reactive structural materials  

NASA Astrophysics Data System (ADS)

The motivations for the research issues addressed in this thesis are based on the needs of the aerospace structural analysis and the design community. The specific focus is related to the characterization and shock induced chemical reactions of multi-functional structural-energetic materials that are also known as the reactive structural materials and their reaction capabilities. Usually motivation for selection of aerospace structural materials is to realize required strength characteristics and favorable strength to weight ratios. The term strength implies resistance to loads experienced during the service life of the structure, including resistance to fatigue loads, corrosion and other extreme conditions. Thus, basically the structural materials are single function materials that resist loads experienced during the service life of the structure. However, it is desirable to select materials that are capable of offering more than one basic function of strength. Very often, the second function is the capability to provide functions of sensing and actuation. In this thesis, the second function is different. The second function is the energetic characteristics. Thus, the choice of dual functions of the material are the structural characteristics and energetic characteristics. These materials are also known by other names such as the reactive material structures or dual functional structural energetic materials. Specifically the selected reactive materials include mixtures of selected metals and metal oxides that are also known as thermite mixtures, reacting intermetallic combinations and oxidizing materials. There are several techniques that are available to synthesize these structural energetic materials or reactive material structures and new synthesis techniques constitute an open research area. The focus of this thesis, however, is the characterization of chemical reactions of reactive material structures that involve two or more solids (or condensed matter). The subject of studies of the shock or thermally induced chemical reactions of the two solids comprising these reactive materials, from first principles, is a relatively new field of study. The published literature on ab initio techniques or quantum mechanics based approaches consists of the ab initio or ab initio-molecular dynamics studies in related fields that contain a solid and a gas. One such study in the literature involves a gas and a solid. This is an investigation of the adsorption of gasses such as carbon monoxide (CO) on Tungsten. The motivation for these studies is to synthesize alternate or synthetic fuel technology by Fischer-Tropsch process. In this thesis these studies are first to establish the procedure for solid-solid reaction and then to extend that to consider the effects of mechanical strain and temperature on the binding energy and chemisorptions of CO on tungsten. Then in this thesis, similar studies are also conducted on the effect of mechanical strain and temperature on the binding energies of Titanium and hydrogen. The motivations are again to understand the method and extend the method to such solid-solid reactions. A second motivation is to seek strained conditions that favor hydrogen storage and strain conditions that release hydrogen easily when needed. Following the establishment of ab initio and ab initio studies of chemical reactions between a solid and a gas, the next step of research is to study thermally induced chemical reaction between two solids (Ni+Al). Thus, specific new studies of the thesis are as follows: (1) Ab initio Studies of Binding energies associated with chemisorption of (a) CO on W surfaces (111, and 100) at elevated temperatures and strains and (b) adsorption of hydrogen in titanium base. (2) Equations of state of mixtures of reactive material structures from ab initio methods. (3) Ab initio studies of the reaction initiation, transition states and reaction products of intermetallic mixtures of (Ni+Al) at elevated temperatures and strains. (4) Press-cure synthesis of Nano-nickel and nano-aluminum based reacti

Zaharieva, Roussislava

388

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high- performance code targeted for GPU accelerators.

Grout, Ray W [ORNL

2012-01-01

389

Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high-performance code targeted for GPU accelerators.

Sankaran, R.; Grout, R.

2012-01-01

390

Simulation of gas absorption into string-of-beads liquid flow with chemical reaction  

NASA Astrophysics Data System (ADS)

This study is an attempt to investigate the chemical absorption of CO2 in aqueous monoethanolamine (MEA) solution in a wetted-wire column consisting of one wire. Computational fluid dynamics method along with volume of fluid model was employed for modeling of two-phase flow, mass transfer and chemical reaction inside the column. The modeling results were compared with available experimental data and very good agreement was achieved. The simulation results showed that the diameter and intervals of liquid beads increases by increasing the gas and liquid flow rates. The beads velocity increases by increasing the liquid flow rate and decreasing mass fraction of MEA in the liquid phase. Also, mass transfer resistance in the liquid phase reduces by formation of the beads. It was concluded that the developed model is capable to predict the effect of operating and physical parameters on the investigated chemical absorption process.

Hosseini, S. M.; Alizadeh, R.; Fatehifar, E.; Alizadehdakhel, A.

2014-04-01

391

Simulation of gas absorption into string-of-beads liquid flow with chemical reaction  

NASA Astrophysics Data System (ADS)

This study is an attempt to investigate the chemical absorption of CO2 in aqueous monoethanolamine (MEA) solution in a wetted-wire column consisting of one wire. Computational fluid dynamics method along with volume of fluid model was employed for modeling of two-phase flow, mass transfer and chemical reaction inside the column. The modeling results were compared with available experimental data and very good agreement was achieved. The simulation results showed that the diameter and intervals of liquid beads increases by increasing the gas and liquid flow rates. The beads velocity increases by increasing the liquid flow rate and decreasing mass fraction of MEA in the liquid phase. Also, mass transfer resistance in the liquid phase reduces by formation of the beads. It was concluded that the developed model is capable to predict the effect of operating and physical parameters on the investigated chemical absorption process.

Hosseini, S. M.; Alizadeh, R.; Fatehifar, E.; Alizadehdakhel, A.

2014-10-01

392

Comparison of the efficiency of a thermo-chemical process to that of a fuel cell process when both involve the same chemical reaction  

E-print Network

and work extraction over a series of temperature steps minimizes irreversibilities that result from the chemical reaction and heat transfer. Results obtained from the numerical calculations on the scheme confirm that when a large number of reactors...

Bulusu, Seshu Periah

2009-05-15

393

Reactions of important OVOCs with hydrogen peroxide and ozone in the tropospheric aqueous phase  

NASA Astrophysics Data System (ADS)

Besides research on the microphysics of cloud droplets and similar aqueous systems in the troposphere, the chemistry of volatile organic compounds (VOCs) from anthropogenic and biogenic sources cannot be neglected for the understanding of tropospheric processes such as the organic particle mass formation. Emissions of biogenic volatile organic compounds (BVOCs) can exceed those of VOCs from anthropogenic sources by a factor of 10[1]. Oxidation products of BVOCs like glyoxal, methylglyoxal, glycolate, glyoxylate and pyruvate, glycolaldehyde, and the unsaturated compounds methacrolein and methyl vinyl ketone are known precursors for less volatile organic substances found in secondary organic aerosols[2,3]. Yet, the main decomposition of these substances is believed to occur via radical reactions. However, Tilgner and Herrmann[2] showed evidence that the turnovers by non-radical reactions with H2O2 or ozone and some non-oxidative organic accretion reactions may even exceed those from the most reactive species in the lower troposphere, the hydroxyl radical OH. This work investigated the reactivities of the atmospheric relevant oxidation products including pyruvic acid and glyoxylic acid towards O3 and H2O2 in the aqueous phase. Furthermore, pH effects were studied by measuring the kinetics of both the protonated and deprotonated forms. The measurements were performed using a UV/VIS-spectrometer (conventional and in addition a Stopped Flow technique) and capillary electrophoresis. In some cases the results indicate higher turnovers of H2O2 and ozone reactions compared to interactions with atmospheric radicals. The experimental data obtained will be presented and their implications for atmospheric multiphase chemistry are discussed. [1] Guenther et al., 1995, Journal of Geophysical Research - Atmosphere, 100(D5), 8873-8892. [2] Tilgner and Herrmann, 2010, Atmospheric Environment, 44, 5415-5422. [3] van Pinxteren et al., 2005, Atmospheric Environment, 39, 4305-4320.

Schöne, Luisa; Weller, Christian; Herrmann, Hartmut

2013-04-01

394

Role of graphene on the surface chemical reactions of BiPO4-rGO with low OH-related defects.  

PubMed

Graphene has been widely introduced into photocatalysis to enhance photocatalytic performance due to its unique physical and chemical properties. However, the effect of graphene on the surface chemical reactions of photocatalysis has not been clearly researched, which is important for photocatalysis because photocatalytic reactions ultimately occur on the catalyst surface. Herein, a two-step solution-phase reaction has been designed to synthesize quasi-core-shell structured BiPO4-rGO cuboids and the role of graphene on the surface chemical reactions was investigated in detail. It was found that the introduced graphene modified the process and the mechanism of the surface chemical reactions. The change mainly originates from the interaction between graphene and the adsorbed O2 molecule. Due to the electron transfer from graphene to adsorbed O2, graphene could tune the interfacial charge transport and efficiently activate molecular oxygen to form O2?(-) anions as the major oxidation species instead of ?OH. In addition, the two-step synthesis approach could efficiently suppress the formation of OH-related defects in the lattice. As a result, the BiPO4-rGO composite exhibited superior photocatalytic activity to BiPO4 and P25, about 4.3 times that of BiPO4 and 6.9 times that of P25. PMID:24056863

Gao, Erping; Wang, Wenzhong

2013-11-21

395

The association reaction between C2H and 1-butyne: a computational chemical kinetics study.  

PubMed

The potential energy surfaces (PES) for the reaction of the C(2)H radical with 1-butyne (C(4)H(6)) have been studied using the CBS-QB3 method. Density functional B3LYP/cc-pVTZ and M06-2X/6-311++G(d,p) calculations have also been performed to analyze the reaction energetics. For detailed theoretical calculation on the total reaction mechanism, the initial association reactions on more and less substituted C atoms of 1-butyne are treated separately followed by a variational transition state theory (VTST) calculation to obtain reaction rates. The successive unimolecular reactions from the association reaction complexes are subjected to Rice-Ramsperger-Kassel-Marcus (RRKM) calculations for reaction rate constants and product branching ratios. The calculated rate constants in the temperature range 70-295 K for both the association reactions are found to be highly temperature dependent at low temperatures, which is contrary to the experimental findings of temperature independent association rates. We have explained this observation with the help of variational nature of the transition states, and we found a "loose" transition state at low temperatures. The calculated product branching ratios for the unimolecular reactions generally agree with the available experimental data, although some channels show a significant method dependency and therefore the correlation with experiment is lost to some extent. Our detailed reaction energetics calculations confirm that the C(2)H + C(4)H(6) reaction proceeds without an entrance barrier and leads to the important products ethynylallene + CH(3), 1,3-hexadiyne + H, 3,4-hexadiene-1-yne + H, 2-ethynyl-1,3-butadiene + H, 3,4-dimethylenecyclobut-1-ene + H and fulvene + H exothermic by 25-75 kcal mol(-1), with strong dependence of the product distribution on the association mode of C(2)H with C(4)H(6), making these reactions fast under low temperature conditions of Titan's atmosphere. Therefore this study can provide a detailed picture of the complex hydrocarbon formation mechanism in the upper atmosphere. PMID:21279199

Mandal, Debasish; Mondal, Bhaskar; Das, Abhijit K

2011-03-14

396

Multicomponent reactive transport simulation of the Elder problem: Effects of chemical reactions on salt plume development  

Microsoft Academic Search

A numerical modeling approach was used to investigate the relevancy of the feedback mechanisms between geochemical reactions and variable density flow during free convection. The problem was studied by reformulating the classic Elder problem as a reactive multicomponent transport problem. It was found that for the studied system, the importance of this feedback decreased with increasing density contrast between intruding

V. E. A. Post; H. Prommer

2007-01-01

397

Some new reaction pathways for the formation of cytosine in interstellar space - A quantum chemical study  

NASA Astrophysics Data System (ADS)

The detection of nucleic acid bases in carbonaceous meteorites suggests that their formation and survival is possible outside of the Earth. Small N-heterocycles, including pyrimidine, purines and nucleobases, have been extensively sought in the interstellar medium. It has been suggested theoretically that reactions between some interstellar molecules may lead to the formation of cytosine, uracil and thymine though these processes involve significantly high potential barriers. We attempted therefore to use quantum chemical techniques to explore if cytosine can possibly form in the interstellar space by radical-radical and radical-molecule interaction schemes, both in the gas phase and in the grains, through barrier-less or low barrier pathways. Results of DFT calculations for the formation of cytosine starting from some of the simple molecules and radicals detected in the interstellar space are being reported. Global and local descriptors such as molecular hardness, softness and electrophilicity, and condensed Fukui functions and local philicity indices were used to understand the mechanistic aspects of chemical reaction. The presence and nature of weak bonds in the molecules and transition states formed during the reaction process have been ascertained using Bader's quantum theory of atoms in molecules (QTAIMs). Two exothermic reaction pathways starting from propynylidyne (CCCH) and cyanoacetylene (HCCCN), respectively, have been identified. While the first reaction path is found to be totally exothermic, it involves a barrier of 12.5 kcal/mol in the gas phase against the lowest value of about 32 kcal/mol reported in the literature. The second path is both exothermic and barrier-less. The later has, therefore, a greater probability of occurrence in the cold interstellar clouds (10-50 K).

Gupta, V. P.; Tandon, Poonam; Mishra, Priti

2013-03-01

398

Reactions of hydroxyl radicals with selected hydrocarbons of importance in atmospheric chemistry  

Microsoft Academic Search

The kinetics of the reactions of OH with i-butanol and t-butanol have been studied by laser flash photolysis-laser induced fluorescence (LP-LIF), under pseudo-first-order conditions. The values, k(OH + i-butanol) equals (9.0 +\\/- 0.9) X 10-12 cm3 molecule-1 s-1 and k(OH + t-butanol) equals 1.8 +\\/- 0.2) X 10-13 cm3 molecule-1 s-1 at 292 K were obtained. As a check on

Sandra M. Saunders; K. J. Hughes; M. J. Pilling; D. L. Baulch; P. I. Smurthwaite

1993-01-01

399

Heat Integration of the Water-Gas Shift Reaction System for Carbon Sequestration Ready IGCC Process with Chemical Looping  

SciTech Connect

Integrated gasification combined cycle (IGCC) technology has been considered as an important alternative for efficient power systems that can reduce fuel consumption and CO2 emissions. One of the technological schemes combines water-gas shift reaction and chemical-looping combustion as post gasification techniques in order to produce sequestration-ready CO2 and potentially reduce the size of the gas turbine. However, these schemes have not been energetically integrated and process synthesis techniques can be applied to obtain an optimal flowsheet. This work studies the heat exchange network synthesis (HENS) for the water-gas shift reaction train employing a set of alternative designs provided by Aspen energy analyzer (AEA) and combined in a process superstructure that was simulated in Aspen Plus (AP). This approach allows a rigorous evaluation of the alternative designs and their combinations avoiding all the AEA simplifications (linearized models of heat exchangers). A CAPE-OPEN compliant capability which makes use of a MINLP algorithm for sequential modular simulators was employed to obtain a heat exchange network that provided a cost of energy that was 27% lower than the base case. Highly influential parameters for the pos gasification technologies (i.e. CO/steam ratio, gasifier temperature and pressure) were calculated to obtain the minimum cost of energy while chemical looping parameters (oxidation and reduction temperature) were ensured to be satisfied.

Juan M. Salazara; Stephen E. Zitney; Urmila M. Diwekara

2010-01-01

400

ABIOTIC REACTIONS MAY BE THE MOST IMPORTANT MECHANISM IN NATURAL ATTENUATION OF CHLORINATED SOLVENTS  

EPA Science Inventory

The EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water was developed with the assumption that natural biological reductive dechlorination was the only important mechanism for destruction of chlorinated solvents and their reduction ...

401

Reaction layer formation and fracture at chemically vapor deposited diamond/metal interfaces  

SciTech Connect

Chemically vapor deposited (CVD) diamond films have been deposited by a microwave enhanced deposition process on metal substrates including titanium, tungsten, molybdenum, and copper. Boundary reaction layers formed at the interface during the growth of the CVD diamond films have been investigated for each of these systems. In these studies, the interface has been exposed by mechanically deforming the metal substrate to cause film delamination. Where the diamond film has adhered to the substrate through the growth process, delamination procedures have been carried out under controlled conditions in order to preserve the integrity of the interfacial species. The exposed interfaces were characterized by x-ray photoelectron spectroscopy, scanning Auger microscopy, secondary electron microscopy, and Raman microprobe spectroscopy. Reaction layers composed of carbides and oxides of the native metal were detected at the interfaces of titanium, tungsten, and molybdenum while only traces of carbon and oxygen were detected at the diamond/copper interface. We believe that both the chemical composition and morphology of the interface influence the adhesive properties of the diamond coating. Correlated investigations of the interfacial surfaces reveal that fracture of the diamond/metal interface occurs discretely at the diamond nucleation plane or within a reaction layer near the diamond interface.

Perry, S.S.; Somorjai, G.A. (Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 (United States))

1994-07-01

402

A spectroscopist's view of energy states, energy transfers, and chemical reactions.  

PubMed

This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments. PMID:17034339

Moore, C Bradley

2007-01-01

403

A Molecular Dynamics Study of Chemical Reactions of Solid Pentaerythritol Tetranitrate at Extreme Conditions  

SciTech Connect

We have carried out density functional based tight binding (DFTB) molecular dynamics (MD) simulation to study energetic reactions of solid Pentaerythritol Tetranitrate (PETN) at conditions approximating the Chapman-Jouguet (CJ) detonation state. We found that the initial decomposition of PETN molecular solid is characterized by uni-molecular dissociation of the NO{sub 2}groups. Interestingly, energy release from this powerful high explosive was found to proceed in several stages. The large portion of early stage energy release was found to be associated with the formation of H{sub 2}O molecules within a few picoseconds of reaction. It took nearly four times as long for majority of CO{sub 2} products to form, accompanied by a slow oscillatory conversion between CO and CO{sub 2}. The production of N{sub 2} starts after NO{sub 2} loses its oxygen atoms to hydrogen or carbon atoms to form H{sub 2}O or CO. We identified many intermediate species that emerge and contribute to reaction kinetics, and compared our simulation with a thermo-chemical equilibrium calculation. In addition, a detailed chemical kinetics of formation of H{sub 2}O, CO, and CO{sub 2} were developed. Rate constants of formations of H{sub 2}O, CO{sub 2} and N{sub 2} were reported.

Wu, C J; Manaa, M R; Fried, L E

2006-05-30

404

When Fairness is Especially Important: Reactions to Being Inequitably Paid in Communal Relationships  

Microsoft Academic Search

This article focuses on when justice is especially important to people and, in doing so, explores the social conditions under\\u000a which the importance of justice may change in social interactions. More specifically, the authors examine how different types\\u000a of relationships affect evaluations of equitable and inequitable situations. It is argued that when people are confronted\\u000a with friends as interaction partners,

Susanne Lidewij Peters; Kees van den Bos

2008-01-01

405

Chemical modifications and bioconjugate reactions of nanomaterials for sensing, imaging, drug delivery and therapy.  

PubMed

As prepared nanomaterials of metals, semiconductors, polymers and carbon often need surface modifications such as ligand exchange, and chemical and bioconjugate reactions for various biosensor, bioanalytical, bioimaging, drug delivery and therapeutic applications. Such surface modifications help us to control the physico-chemical, toxicological and pharmacological properties of nanomaterials. Furthermore, introduction of various reactive functional groups on the surface of nanomaterials allows us to conjugate a spectrum of contrast agents, antibodies, peptides, ligands, drugs and genes, and construct multifunctional and hybrid nanomaterials for the targeted imaging and treatment of cancers. This tutorial review is intended to provide an introduction to newcomers about how chemical and bioconjugate reactions transform the surface of nanomaterials such as silica nanoparticles, gold nanoparticles, gold quantum clusters, semiconductor quantum dots, carbon nanotubes, fullerene and graphene, and accordingly formulate them for applications such as biosensing, bioimaging, drug and gene delivery, chemotherapy, photodynamic therapy and photothermal therapy. Nonetheless, controversial reports and our growing concerns about toxicity and pharmacokinetics of nanomaterials suggest the need for not only rigorous in vivo experiments in animal models but also novel nanomaterials for practical applications in the clinical settings. Further reading of original and review articles cited herein is necessary to buildup in-depth knowledge about the chemistry, bioconjugate chemistry and biological applications of individual nanomaterials. PMID:24220322

Biju, Vasudevanpillai

2014-02-01

406

Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques  

NASA Astrophysics Data System (ADS)

The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule atomic force microscopy (AFM) techniques, as shown here, can probe dynamic rearrangements within an enzyme's active site which cannot be resolved with any other current structural biological technique. Furthermore, our work at the single bond level directly demonstrates that thiol/disulfide exchange in proteins is a force-dependent chemical reaction. Our findings suggest that mechanical force plays a role in disulfide reduction in vivo, a property which has never been explored by traditional biochemistry. 1.-Wiita, A.P., Ainavarapu, S.R.K., Huang, H.H. and Julio M. Fernandez (2006) Force-dependent chemical kinetics of disulfide bond reduction observed with single molecule techniques. Proc Natl Acad Sci U S A. 103(19):7222-7 2.-Wiita, A.P., Perez-Jimenez, R., Walther, K.A., Gräter, F. Berne, B.J., Holmgren, A., Sanchez-Ruiz, J.M., and Fernandez, J.M. (2007) Probing the chemistry of thioredoxin catalysis with force. Nature, 450:124-7.

Fernandez, Julio M.

2008-03-01

407

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)  

EPA Science Inventory

The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

408

Effect of nonequilibrium chemical reactions on the concentration distribution of alkali atoms in the boundary layer  

SciTech Connect

The distribution of alkali metal atoms (potassium) in the boundary layer of combustion products in a laboratory setup with a Mekker burner was studied. It was found that the experimentally determined and computed concentrations are in good agreement with one another and substantially exceed the values corresponding to the limiting cases of both equilibrium and frozen chemical reactions. A qualitative explanation of this effect, which, generally speaking, can occur in large-scale setups, is given based on an analysis of the computational results.

Benilov, M.S.; Vasil'eva, I.A.; Kovbasyuk, V.I.; Kosov, V.F.; Kosova, R.V.; Rogov, B.V.; Sinel'shchikov, V.A.; Sokolova, I.A.; Tirskii, G.A.

1986-05-01

409

Density Functional Study for Chemical Reaction between Cr and Fe with Sodium Diethyldithiocarbamate (NaDDC)  

NASA Astrophysics Data System (ADS)

Analytical chemistry in the perspective of ab initio molecular orbital calculation is introduced by investigating the chemical reaction between transition metals Cr and Fe with sodium diethyldithiocarbamate (NaDDC), a complexing agent to detect and extract Cr in human blood sample. Using density functional theory—based calculations, we determine the stable structure of the Cr-DDC and Fe-DDC complexes and obtain its dissociation energies. We found dissociation energy values of -3.24 and -2.67 eV for Cr and Fe complexes, respectively; and hence the formation of the former complex is more favorable than the formation of the latter.

Setiyanto, Henry; Muhida, Rifki; Kishi, Tomoya; Rahman, Md. Mahmudur; Dipojono, Hermawan K.; Diño, Wilson A.; Matsumoto, Shigeno; Kasai, Hideaki

410

A phenomenological study of heterogeneous chemical reactions of mercuric chloride on heated stainless steel surfacesa)  

NASA Astrophysics Data System (ADS)

We have made the first measurements of the products of surface chemical reactions of mercuric chloride on heated stainless steel using the technique of electron-energy-loss spectroscopy as an analytic tool. We find that HgCl2 reacts with hydrogen in the stainless steel to form hydrochloric acid HCl. Under our experimental conditions HCl becomes the cominant species observed in our spectra at surface temperatures greater than about 150 °C. The possible consequences of our observation on the efficiency of mercuric halide lasers is discussed. (AIP)

Wang, R.-G.; Dillon, M. A.; Spence, David

1983-07-01

411

Quantum-chemical calculations on a novel reaction mechanism of CNN with NO  

NASA Astrophysics Data System (ADS)

Quantum-chemical calculations of the possible interaction between CNN and NO have been performed at the CCSD(T)/aug-cc-PVTZ//B3LYP/6-31++G(d,p) level of theory. Fourteen conformers corresponding to local minima of potential energy and sixteen transition structures are located, and various possible reaction paths are probed. Products P3 - NCO + N 2 - and P4 - N 2O + CN - were the two leading channels with slight energy barriers as compared to the reactants CNN + NO. Employing the Fukui functions and HSAB theory, we are able to rationalize the calculated outcomes.

Chen, Hui-Lung; Li, Han-Jung; Ho, Jia-Jen

2007-07-01

412

Heat and Mass Transfer in Unsteady Rotating Fluid Flow with Binary Chemical Reaction and Activation Energy  

PubMed Central

In this study, the Spectral Relaxation Method (SRM) is used to solve the coupled highly nonlinear system of partial differential equations due to an unsteady flow over a stretching surface in an incompressible rotating viscous fluid in presence of binary chemical reaction and Arrhenius activation energy. The velocity, temperature and concentration distributions as well as the skin-friction, heat and mass transfer coefficients have been obtained and discussed for various physical parametric values. The numerical results obtained by (SRM) are then presented graphically and discussed to highlight the physical implications of the simulations. PMID:25250830

Awad, Faiz G.; Motsa, Sandile; Khumalo, Melusi

2014-01-01

413

A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction  

NASA Technical Reports Server (NTRS)

This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

Lian, Yongsheng; Xu, Kun

1999-01-01

414

ToxAlerts: A Web Server of Structural Alerts for Toxic Chemicals and Compounds with Potential Adverse Reactions  

PubMed Central

The article presents a Web-based platform for collecting and storing toxicological structural alerts from literature and for virtual screening of chemical libraries to flag potentially toxic chemicals and compounds that can cause adverse side effects. An alert is uniquely identified by a SMARTS template, a toxicological endpoint, and a publication where the alert was described. Additionally, the system allows storing complementary information such as name, comments, and mechanism of action, as well as other data. Most importantly, the platform can be easily used for fast virtual screening of large chemical datasets, focused libraries, or newly designed compounds against the toxicological alerts, providing a detailed profile of the chemicals grouped by structural alerts and endpoints. Such a facility can be used for decision making regarding whether a compound should be tested experimentally, validated with available QSAR models, or eliminated from consideration altogether. The alert-based screening can also be helpful for an easier interpretation of more complex QSAR models. The system is publicly accessible and tightly integrated with the Online Chemical Modeling Environment (OCHEM, http://ochem.eu). The system is open and expandable: any registered OCHEM user can introduce new alerts, browse, edit alerts introduced by other users, and virtually screen his/her data sets against all or selected alerts. The user sets being passed through the structural alerts can be used at OCHEM for other typical tasks: exporting in a wide variety of formats, development of QSAR models, additional filtering by other criteria, etc. The database already contains almost 600 structural alerts for such endpoints as mutagenicity, carcinogenicity, skin sensitization, compounds that undergo metabolic activation, and compounds that form reactive metabolites and, thus, can cause adverse reactions. The ToxAlerts platform is accessible on the Web at http://ochem.eu/alerts, and it is constantly growing. PMID:22876798

2012-01-01

415

Review of Chemical Reactions in the NO Reduction by CO on Platinum/alumina Catalysts  

NASA Astrophysics Data System (ADS)

The emissions of nitric oxide and carbon monoxide from internal combustion engines generate a large impact on the environment and on people's health. Catalytic reduction of these species using platinum group metals has already shown significant potential for emissions control. Since catalysts often use carbon monoxide to reduce nitric oxide in these devices, accurate models of their interaction are required to advance catalyst simulations in order to meet increasingly stringent emissions regulations. As a result, this paper reviews the literature of the NO-CO reaction over platinum in order to develop more precise detailed and global reaction mechanisms for use in exhaust after-treatment modeling activities. Moreover, it is found that the reaction between NO and CO over platinum yields carbon dioxide and nitrogen as main products and nitrous oxide as an important side product. Hence, this paper additionally describes the mechanism for nitrous oxide production in advance of greenhouse gas regulations.

Srinivasan, Anand; Depcik, Christopher

2012-02-01

416

The Importance of IgG Avidity and the Polymerase Chain Reaction in Treating Toxoplasmosis during Pregnancy: Current Knowledge  

PubMed Central

A brief report on the nature and epidemiology of T. gondii infection is firstly presented. The importance of the specific IgG avidity test and polymerase chain reaction (PCR) for toxoplasmosis is discussed, along with their significance and importance as auxiliary methods for determining the most likely time for the initial infection by this coccidian and for defining the therapeutic strategy. Lastly, practical comments are made in relation to the classical therapeutic regimens, with special attention to the indications for fetal treatment, when this is necessary. PMID:24191157

Bortoletti Filho, Joao; Carvalho, Natalia da Silva; Helfer, Talita Micheletti; Nogueira Serni, Priscila de Oliveira; Nardozza, Luciano Marcondes Machado; Moron, Antonio Fernandes

2013-01-01

417

Reprint of: A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction  

NASA Astrophysics Data System (ADS)

This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)?A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O?B(aq)+H+ with a chemical reaction rate ?A. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(?0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

Nagaosa, Ryuichi S.

2014-08-01

418

Importance of the polymerase chain reaction in the study of hepatitis C virus infection  

Microsoft Academic Search

Summary  Recently, the principal etiological agent of parenterally transmitted non-A, non-B hepatitis was molecularly cloned from the\\u000a plasma of an experimentally infected chimpanzee and has been named hepatitis C virus. Determination of the complete nucleotide\\u000a sequence of the hepatitis C virus genome was a crucial step in preparing the way for future study of this medically important\\u000a human pathogen. Due to

Roger H. Miller; Jens Bukh; Robert H. Purcell

1993-01-01

419

Dynamic Transition in the Structure of an Energetic Crystal during Chemical Reactions at Shock Front Prior to Detonation  

E-print Network

Dynamic Transition in the Structure of an Energetic Crystal during Chemical Reactions at Shock crystal that bond-bending of nitro group in TATB molecule closes the HOMO-LUMO gap and have speculated that reaction may proceed at super- sonic speed [15]. Atomistic-level understanding of the structure of shock

Southern California, University of

420

The Locomotor Activity of Fish: An Analogy to the Kinetics of an Opposed First-Order Chemical Reaction  

Microsoft Academic Search

The kinetic behavior of a laboratory population of bluegill (Lepomis macrochirus) under defined laboratory conditions is shown to be analogous to the reaction kinetics described by a population of molecules engaged in an opposed (reversible) first-order reaction. Thus as in chemical kinetics, the locomotor activity of fish can be described quantitatively in the form of rate constants.

Erik G. Ellgaard; Kerry S. Bloom; Anthony A. Malizia JR; Gerald E. Gunning; Richard E. Jensen

1975-01-01

421

Local regularity and non-recrossing path in transition state--a new strategy in chemical reaction theories  

E-print Network

Local regularity and non-recrossing path in transition state--a new strategy in chemical reaction theories T. Komatsuzaki*, R.S. Berry Department of Chemistry, The University of Chicago, Chicago, IL 60637-Jones cluster to demonstrate how one can choose a non-recrossing reaction path in phase space along which

Berry, R. Stephen

422

Chemistry in disks. IV. Benchmarking gas-grain chemical models with surface reactions  

NASA Astrophysics Data System (ADS)

Context. We describe and benchmark two sophisticated chemical models developed by the Heidelberg and Bordeaux astrochemistry groups. Aims: The main goal of this study is to elaborate on a few well-described tests for state-of-the-art astrochemical codes covering a range of physical conditions and chemical processes, in particular those aimed at constraining current and future interferometric observations of protoplanetary disks. Methods: We considered three physical models: a cold molecular cloud core, a hot core, and an outer region of a T Tauri disk. Our chemical network (for both models) is based on the original gas-phase osu_03_2008 ratefile and includes gas-grain interactions and a set of surface reactions for the H-, O-, C-, S-, and N-bearing molecules. The benchmarking was performed with the increasing complexity of the considered processes: (1) the pure gas-phase chemistry, (2) the gas-phase chemistry with accretion and desorption, and (3) the full gas-grain model with surface reactions. The chemical evolution is modeled within 109 years using atomic initial abundances with heavily depleted metals and hydrogen in its molecular form. Results: The time-dependent abundances calculated with the two chemical models are essentially the same for all considered physical cases and for all species, including the most complex polyatomic ions and organic molecules. This result, however, required a lot of effort to make all necessary details consistent through the model runs, e.g., definition of the gas particle density, density of grain surface sites, or the strength and shape of the UV radiation field. Conclusions: The reference models and the benchmark setup, along with the two chemical codes and resulting time-dependent abundances are made publicly available on the internet. This will facilitate and ease the development of other astrochemical models and provide nonspecialists with a detailed description of the model ingredients and requirements to analyze the cosmic chemistry as studied, e.g., by (sub-) millimeter observations of molecular lines. Figures 1-5 and Tables 1-3 are only available in electronic form at http://www.aanda.org

Semenov, D.; Hersant, F.; Wakelam, V.; Dutrey, A.; Chapillon, E.; Guilloteau, St.; Henning, Th.; Launhardt, R.; Piétu, V.; Schreyer, K.

2010-11-01

423

Interface reactions during processing of chemical vapor deposited yttrium oxide high-k dielectrics  

Microsoft Academic Search

High dielectric constant (high-k) insulators are important for advanced MOS devices to limit gate leakage and increase gate capacitance. Reactions between high-k's and the substrate during deposition or post-deposition processing lead to an increase in the equivalent oxide thickness, and the mechanisms that control the changes need to be well understood. We investigate yttrium-based high-k dielectrics formed by oxygen plasma

Dong Niu

2002-01-01

424

Astrophysically Important Reaction Rates For Novae And X-ray Bursts From Proton Breakup At Intermediate Energies  

SciTech Connect

We discuss the use of one-nucleon removal reactions of loosely bound nuclei at intermediate energies as an indirect method in nuclear astrophysics. The breakup reactions are proved to be good spectroscopic tools and can be used to study a large number of loosely bound proton- or neutron-rich nuclei over a wide range of beam energies. As peripheral processes, they can be used to extract asymptotic normalization coefficients (ANCs) from which non-resonant capture reaction rates of astrophysical interest can be calculated parameter free. In this talk, we present results of a proton-breakup experiment carried out at GANIL (France) with a cocktail beam centered around {sup 23}Al at 50 MeV/nucleon. Momentum distributions of the breakup fragments, inclusive and in coincidence with gamma rays detected by EXOGAM Germanium clover array, were measured in the focal plan of SPEG energy-loss spectrometer. We present in particular the investigations of reaction rates for {sup 22}Mg(p,{gamma}){sup 23}Al and {sup 23}Al(p,{gamma}){sup 24}Si important for novae and X-ray bursts, respectively.

Banu, A.; Trache, L. [Cyclotron Institute, Texas A and M University, College Station, Texas 77843-3366 (United States); National Institute of Physics and Nuclear Engineering, 'Horia Hulubei' (IFIN-HH), R-077125 Magurele-Bucharest (Romania); Carstoiu, F.; Negoita, F.; Rotaru, F. [National Institute of Physics and Nuclear Engineering, 'Horia Hulubei' (IFIN-HH), R-077125 Magurele-Bucharest (Romania); Orr, N. A.; Achouri, N. L.; Laurent, B. [Laboratoire de Physique Corpusculaire, IN2P3-CNRS, ISMRA et Universite, F-14050 Caen (France); Bonaccorso, A. [Instituto Nazionale di Fisica Nucleare, Sez. Di Pisa, I-56127 Pisa (Italy); Catford, W. N.; Patterson, N.; Thomas, J. S. [Department of Physics, University of Surrey, Guildford GU2 5XH (United Kingdom); Chartier, M.; Fernandez-Dominguez, B.; Paschalis, S.; Pietras, B. [Oliver Lodge Laboratory, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Freer, M. [School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom); Gaudefroy, L.; Roussel-Chomaz, P. [Grand Accelerateur d'Ions Lourds, BP 55027, 14076 Caen Cedex 5 (France); Horoi, M. [Department of Physics, Central Michigan University, Mount Pleasant, Michigan 48859 (United States)

2010-11-24

425

Thermochemical modeling of temperature controlled shock-induced chemical reactions in multifunctional energetic structural materials under shock compression  

NASA Astrophysics Data System (ADS)

Multifunctional energetic structural materials (MESMs) are a new class of energetic materials which release energy due to exothermic chemical reactions initiated under shock loading conditions. In order to analyze shock-induced chemical reactions (SICR) for MESMs, theoretical models have been developed to calculate the Hugoniot data which include the heat released by shock temperature controlled reactions. The temperature rise of porous materials due to shock compression is first calculated using a constant volume and pressure adjustment. Then the Arrhenius reaction rate and Avrami-Erofeev kinetic models are used to calculate the extent of reaction of MESMs under shock compression. Thermochemical models for shock-induced reactions, in which the reaction efficiency is considered, are given by combining the shock temperature rise with the chemical reaction kinetics. The Hugoniot relations and temperatures are calculated by using the proposed method. The models developed have been validated against the experimental SICR data involving Fe2O3/Al, Al/Ni, and Ti/Ni mixtures. It has been shown that the theoretical calculations correlate reasonably well with the corresponding experimental and simulation results. The models presented can be used to predict the reaction results of MESMs over a wide range of pressure satisfactorily.

Zhang, X. F.; Shi, A. S.; Zhang, J.; Qiao, L.; He, Y.; Guan, Z. W.

2012-06-01

426

Ultrafast electron diffraction and direct observation of transient structures in a chemical reaction  

PubMed Central

Ultrafast electron diffraction is a unique method for the studies of structural changes of complex molecular systems. In this contribution, we report direct ultrafast electron diffraction study of the evolution of short-lived intermediates in the course of a chemical change. Specifically, we observe the transient intermediate in the elimination reaction of 1,2-diiodotetrafluoroethane (C2F4I2) to produce the corresponding ethylene derivative by the breakage of two carbon–iodine, C—I, bonds. The evolution of the ground-state intermediate (C2F4I radical) is directly revealed in the population change of a single chemical bond, namely the second C—I bond. The elimination of two iodine atoms was shown to be nonconcerted, with reaction time of the second C—I bond breakage being 17 ± 2 ps. The structure of the short-lived C2F4I radical is more favorable to the classical radical structure than to the bridged radical structure. This leap in our ability to record structural changes on the ps and shorter time scales bodes well for many future applications in complex molecular systems. PMID:9892634

Cao, Jianming; Ihee, Hyotcherl; Zewail, Ahmed H.

1999-01-01

427

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2012 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2012-01-01

428

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

Code of Federal Regulations, 2013 CFR

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2013-01-01

429

15 CFR 713.1 - Prohibition on exports and imports of Schedule 2 chemicals to and from States not Party to the CWC.  

...on exports and imports of Schedule 2 chemicals to and from States not Party to the...SECURITY, DEPARTMENT OF COMMERCE CHEMICAL WEAPONS CONVENTION REGULATIONS ACTIVITIES INVOLVING SCHEDULE 2 CHEMICALS § 713.1 Prohibition on...

2014-01-01

430

Study of astrophysically important resonant states in 26Si by the 28Si(4He,6He)26Si reaction  

NASA Astrophysics Data System (ADS)

PoS(NIC-IX)024 , b, H. Yamaguchia, J. J. Hea , A. Saitoa , Y. Wakabayashia, H. Fujikawaa, G. The emission of 1.809 MeV gamma-ray from the first excited state of 26 Mg followed by beta- decay of 26 Al in its ground state (denoted as 26 Alg.s. ) has been identified by gamma-ray telescopes such the Compton Gamma-Ray Observatory (CGRO) [1]. To resolve controversy over the pos- sible sources of the observational 1.809 MeV gamma-rays, one needs accurate knowledge of the production rate of 26 Al. The 25 Al(p,?)26Si reaction which is the competition reaction for produc- tion of 26 Alg.s. is one of the important subjects to be investigated. In this work, the astrophysically important 26 Si states above the proton threshold were studied via the 28 Si(4 He,6 He)26 Si reaction. We have preformed an angular distribution measurement using the high resolution QDD spectro- graph (PA) at Center for Nuclear Study (CNS), University of Tokyo. The experimental results and data analysis will be presented.

Kwon, Young Kwan; Lee, C. S.; Moon, J. Y.; Lee, J. H.; Kim, J. Y.; Kubono, S.; Iwasa, N.; Inafiki, K.; Yamaguchi, H.; He, J. J.; Saito, A.; Wakabayashi, Y.; Fukijawa, H.; Amadio, G.; Khiem, L. H.; Tanaka, M.; Chen, A.; Kato, S.

431

The effect of amoxycillin on salivary nitrite concentrations: an important mechanism of adverse reactions?  

PubMed Central

Broad spectrum antibiotics are known to predispose towards oral candidiasis and gastroenteritis. Oral nitrite synthesis by commensal bacteria may be important in protecting the mouth and lower intestine from pathogenic organisms, including Candida albicans. The effect of 2 days administration of the broad spectrum antibiotic amoxycillin on salivary nitrite concentration, following a 200 mg potassium nitrate oral load, was studied in 10 healthy volunteers. The Cmax fell by 40% and the AUC was reduced by 1227 microM h (43%, 95% CI 273, 2181, P < 0.006) in the antibiotic treated group when compared with control. These findings suggest that destruction of nitrate reductase containing bacteria in the mouth by antibiotics may explain an increased incidence of infection with Candida and other pathogens. PMID:7640157

Dougall, H T; Smith, L; Duncan, C; Benjamin, N

1995-01-01

432

Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere  

NASA Technical Reports Server (NTRS)

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

Evans, Christopher

2013-01-01

433

Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere  

NASA Technical Reports Server (NTRS)

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

Evans, Christopher

2013-01-01

434

Influence of exothermic chemical reactions on laser-induced shock waves.  

PubMed

Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (>750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time. PMID:25182866

Gottfried, Jennifer L

2014-10-21

435

Performance and cost of energy transport and storage systems for dish applications using reversible chemical reactions  

NASA Astrophysics Data System (ADS)

The use of reversible chemical reactions for energy transport and storage for parabolic dish networks is considered. Performance and cost characteristics are estimated for systems using three reactions (sulfur-trioxide decomposition, steam reforming of methane, and carbon-dioxide reforming of methane). Systems are considered with and without storage, and in several energy-delivery configurations that give different profiles of energy delivered versus temperature. Cost estimates are derived assuming the use of metal components and of advanced ceramics. (The latter reduces the costs by three- to five-fold). The process that led to the selection of the three reactions is described, and the effects of varying temperatures, pressures, and heat exchanger sizes are addressed. A state-of-the-art survey was performed as part of this study. As a result of this survey, it appears that formidable technical risks exist for any attempt to implement the systems analyzed in this study, especially in the area of reactor design and performance. The behavior of all components and complete systems under thermal energy transients is very poorly understood. This study indicates that thermochemical storage systems that store reactants as liquids have efficiencies below 60%, which is in agreement with the findings of earlier investigators.

Schredder, J. M.; Fujita, T.

1984-10-01

436

Chemical morphogenesis: recent experimental advances in reaction-diffusion system design and control  

PubMed Central

In his seminal 1952 paper, Alan Turing predicted that diffusion could spontaneously drive an initially uniform solution of reacting chemicals to develop stable spatially periodic concentration patterns. It took nearly 40 years before the first two unquestionable experimental demonstrations of such reaction–diffusion patterns could be made in isothermal single phase reaction systems. The number of these examples stagnated for nearly 20 years. We recently proposed a design method that made their number increase to six in less than 3 years. In this report, we formally justify our original semi-empirical method and support the approach with numerical simulations based on a simple but realistic kinetic model. To retain a number of basic properties of real spatial reactors but keep calculations to a minimal complexity, we introduce a new way to collapse the confined spatial direction of these reactors. Contrary to similar reduced descriptions, we take into account the effect of the geometric size in the confinement direction and the influence of the differences in the diffusion coefficient on exchange rates of species with their feed environment. We experimentally support the method by the observation of stationary patterns in red-ox reactions not based on oxihalogen chemistry. Emphasis is also brought on how one of these new systems can process different initial conditions and memorize them in the form of localized patterns of different geometries. PMID:23919126

Szalai, Istvan; Cuinas, Daniel; Takacs, Nandor; Horvath, Judit; De Kepper, Patrick

2012-01-01

437

Chemical reactions between CF2HCl and NH3 induced by IR double-beam excitation  

NASA Astrophysics Data System (ADS)

Infrared multiphoton dissociation experiments with two wavelengths in different mixtures of chlorodifluoromethane and ammonia have been carried out. It is shown that the presence of ammonia in the sample induces a decrease in the chlorodifluoromethane dissociation yield. It has been observed that the distinct chemical reaction channels are differently activated as the time delay between the two laser pulses is varied. The ratio of the obtained products in the infrared multiphoton dissociation changes with the composition of the initial mixture and are not compatible with the mechanism suggested by Sugita and Arai for this reaction in single IR wavelength excitation if it is assumed to be the only contributing mechanism other than that for direct CF2HCl dissociation and subsequent C2F4 formation from the resulting CF2 radicals. It appears that, although for simultaneous two-wavelength irradiation the presence of an accumulated solid NH4Cl deposit does not significantly influence the reaction, this is no longer the case when time delays are introduced between the two beams.

Sigüenza, C. L.; Simeonov, S. A.; Díaz, L.; González-Díaz, P. F.

1993-06-01

438

JASPERSE CHEM 341 TEST 2 VERSION 4 Ch. 5 The Study of Chemical Reactions  

E-print Network

reactions, rearrangements are likely to occur in: a) SN1 reactions only b) SN2 reactions only c) E1 reactions only d) Both SN1 and E1 reactions e) Both SN2 and E2 reactions #12; bromide as leaving group 16. Consider the SN2 reaction shown below. Assuming no other changes, what effect

Jasperse, Craig P.

439

Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.  

PubMed

(1) H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH4 (+) ). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd. PMID:24942984

Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

2014-11-01

440

Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product  

SciTech Connect

Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

2011-05-01

441

Chemical reactions induced in frozen formic acid by heavy ion cosmic rays  

NASA Astrophysics Data System (ADS)

We studied the effects produced by the interaction of heavy ion cosmic rays with interstellar and cometary organic molecules in the solid phase. Formic acid (HCOOH) ice at 15 K was irradiated by 267-MeV 56Fe22+ ions and the chemical evolution was analysed using Fourier transform infrared spectroscopy. The destruction cross-section of HCOOH and the formation cross-sections of the produced molecular species have been determined; the sputtering yield values are also discussed. The most abundant chemical species formed by Fe ion irradiation are CO, CO2 and H2O. The half-life of frozen formic acid molecules in the interstellar medium, as a result of interaction with the different cosmic ray constituents, is evaluated to be 108 yr, considering that the destruction cross-section ?d of heavy ions is ruled by a power law as a function of the electronic stopping power Se (i.e. ?d ˜ S3/2e). Moreover, a complementary study based on mass spectrometry data from the literature has been performed, in order to understand the HCOOH molecule radiolysis, the desorption of its product and the chemical reaction pathways in ice.

Andrade, Diana P. P.; de Barros, Ana L. F.; Pilling, Sérgio; Domaracka, Alicja; Rothard, Hermann; Boduch, Philippe; da Silveira, Enio F.

2013-04-01

442

Probabilistic Health Risk Assessment of Chemical Mixtures: Importance of Travel Times and Connectivity  

NASA Astrophysics Data System (ADS)

Subsurface contamination cases giving rise to groundwater pollutions are extensively found in all industrialized countries. Under this pressure, risk assessment methods play an important role in population protection by (1) quantifying the potential impact on human health of an aquifer contamination and (2) helping and driving decisions of groundwater-resource managers. Many reactive components such as chlorinated solvents or nitrates potentially experience attenuation processes under common geochemical conditions. This represents an attractive and extensively used remediation solution but leads often to the production of by-products before to reach a harmless chemical form. This renders mixtures of contaminants a common issue for groundwater resources managers. In this case, the threat posed by these contaminants to human health at a given sensitive location greatly depends on the competition between reactive and advective-dispersive characteristic times. However, hydraulic properties of the aquifer are known to be spatially variable, which can lead to the formation of preferential flow channels and fast contamination pathways. Therefore, the uncertainty on the spatial distribution of the aquifer properties controlling the plume travel time may then play a particular role in the human health risk assessment of chemical mixtures. We investigate here the risk related to a multispecies system in response to different degrees of heterogeneity of the hydraulic conductivity (K or Y =ln(K)). This work focuses on a Perchloroethylene (PCE) contamination problem followed by the sequential first-order production/biodegradation of its daughter species Trichloroethylene (TCE), Dichloroethylene (DCE) and Vinyl Chlorine (VC). For this specific case, VC is known to be a highly toxic contaminant. By performing numerical experiments, we evaluate transport through three-dimensional mildly (?Y 2=1.0) and highly (?Y 2=4.0) heterogeneous aquifers. Uncertainty on the hydraulic conductivity field is considered through a Monte Carlo scheme, and statistics of the total risk for human health (RT) related to the mixtures of the four carcinogenic plumes are evaluated. Results show two distinct spatiotemporal behavior of the RT estimation. Simulations in highly heterogeneous aquifers display a lower mean of RT close to the injection and higher further away. We explain this by the distinct ranges of travel times and connectivity metrics related to the two sets of aquifers. A high ?Y 2 trends to decrease the travel time (and increase the connectivity). Early travel times, associated to channeling effects, are intuitively perceived as an indicator for high risk. However, in our case, early travel times lead a limited production of highly toxic daughter species and a lower total risk. Our results reflect then the interplay between the characteristic reactive time for each component and the characteristic travel time of the plume since the production of VC depends on these factors.

Henri, Christopher V.; Fernàndez-Garcia, Daniel; de Barros, Felipe P. J.

2014-05-01

443

A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.  

PubMed

Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases. PMID:19791885

Gallis, Michael A; Bond, Ryan B; Torczynski, John R

2009-09-28